WO2014097993A1 - Bottom layer film-formation composition of self-organizing film containing polycyclic organic vinyl compound - Google Patents
Bottom layer film-formation composition of self-organizing film containing polycyclic organic vinyl compound Download PDFInfo
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- WO2014097993A1 WO2014097993A1 PCT/JP2013/083492 JP2013083492W WO2014097993A1 WO 2014097993 A1 WO2014097993 A1 WO 2014097993A1 JP 2013083492 W JP2013083492 W JP 2013083492W WO 2014097993 A1 WO2014097993 A1 WO 2014097993A1
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- ADTGZIJRMJKELC-UHFFFAOYSA-N CC(C)(C)C(NCCO)=O Chemical compound CC(C)(C)C(NCCO)=O ADTGZIJRMJKELC-UHFFFAOYSA-N 0.000 description 1
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- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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- B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
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- B05D1/38—Successively applying liquids or other fluent materials, e.g. without intermediate treatment with intermediate treatment
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- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
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Definitions
- the present invention is an underlayer film forming composition for forming an underlayer film of a self-assembled film, and the underlayer film formed by thermal firing of the composition is a liquid crystal display, a recording material for a hard disk, a solid-state imaging device, a solar cell Underlayer film formation used for panels, light-emitting diodes, organic light-emitting devices, luminescent films, fluorescent films, MEMS, actuators, antireflection materials, resists, resist underlayer films, resist overlayer films, or nanoimprint templates (molds) Relates to the composition.
- this invention relates to the formation method of the pattern structure which forms the self-organization film
- Self-assembled films with nanoscale repeat structures are known to have different properties from normal homogeneous films, and self-assembled films with nanoscale repeat structures using block polymers have been proposed. ing.
- nonpatent literature 1 the property which mixed the organic photochromic material in the non-curable polystyrene / poly (methyl methacrylate) copolymer is reported.
- Nonpatent literature 2 nanopatterning characteristics using plasma etching using non-curable polystyrene / poly (methyl methacrylate) copolymer have been reported.
- Patent Document 3 nanopatterning properties using non-curable polystyrene / poly (methyl methacrylate) copolymers have been reported (Patent Document 3).
- a thin film coating composition using a block polymer comprising a polymer chain having a fluorine-containing vinyl monomer unit and a polymer chain having at least a vinyl monomer unit having a silyl group is disclosed (see Patent Document 1). ).
- a pattern forming method for forming a pattern in a block polymer layer by regularly arranging a plurality of segments constituting the block polymer is disclosed (see Patent Document 2).
- a film-forming composition comprising a block polymer, a crosslinking agent and an organic solvent is disclosed.
- pattern information can be input to the lower layer film (for example, using an organic film) in order to pattern the block polymer into a cylinder shape.
- the polymer chain (A) component and the polymer chain (B) component of the (self-assembled) film-forming composition using the block polymer can be arranged at desired positions, respectively (see Patent Document 3 above) ).
- the present invention provides a composition for forming a lower layer film that is advantageously used to facilitate the arrangement of a self-assembled film in a desired vertical pattern when forming a self-assembled film using a block polymer or the like. To do.
- the present invention also provides a lower layer film of the self-assembled film that does not cause intermixing (layer mixing) with the upper self-assembled film and can form a vertical pattern on the self-assembled film.
- a composition is provided.
- a composition for forming a lower film of a self-assembled film comprising a polymer having a unit structure of a polycyclic aromatic vinyl compound of 0.2 mol% or more per total unit structure of the polymer ,
- the polymer has a unit structure of an aromatic vinyl compound of 20 mol% or more per total unit structure of the polymer, and a unit structure of a polycyclic aromatic vinyl compound per total unit structure of the aromatic vinyl compound
- a composition for forming a lower layer film of a self-assembled film according to the first aspect characterized in that the polymer is a polymer having 1 mol% or more of
- the aromatic vinyl compound includes vinyl naphthalene, acenaphthylene, or vinyl carbazole, each of which may be substituted, and the polycyclic aromatic vinyl compound is vinyl naphthalene, acenaphthylene, or vinyl carbazole,
- the underlayer film forming composition for a self-assembled film according to any one of the second aspect to the fourth aspect, which may be vinyl naphthalene, acenaphthylene, or vinyl carbazole,
- the aromatic vinyl compound is composed only of a polycyclic aromatic vinyl compound, and the aromatic vinyl compound is vinyl naphthalene, acenaphthylene, or vinyl carbazole, each of which may be substituted.
- the underlayer film forming composition for a self-assembled film according to any one of the fifth aspects As a seventh aspect, the self-assembled film according to any one of the second to sixth aspects, wherein the polymer has a unit structure of an aromatic vinyl compound of 60 to 95 mol% per total unit structure of the polymer.
- the underlayer film forming composition for a self-assembled film according to the eighth aspect in which the cross-linking group is a hydroxy group, an epoxy group, a protected hydroxy group, or a protected carboxyl group
- the underlayer film forming composition for a self-assembled film according to any one of the first aspect to the ninth aspect further including a crosslinking agent
- the underlayer film forming composition for a self-assembled film according to any one of the first aspect to the tenth aspect further comprising an acid or an acid generator,
- the self-assembled film includes, as a unit structure, an organic polymer chain (A) containing an organic monomer (a) as
- the underlayer film formation of the self-assembled film according to any one of the first aspect to the eleventh aspect, which is a film made of a block polymer including a polymer chain (B) bonded to the polymer chain (A) Composition
- the block polymer contains polystyrene (A) and polymethyl methacrylate (B), polystyrene (A) and polyisoprene (B), polystyrene (A) and polybutadiene (B), polystyrene (A) and polydimethyl.
- the underlayer film of the self-assembled film according to the twelfth aspect which is a block polymer composed of a combination of siloxane (B), polystyrene (A) and polyethylene oxide (B), or polystyrene (A) and polyvinylpyridine (B).
- Forming composition As a fourteenth aspect, a step of applying and baking the underlayer film forming composition of the self-assembled film according to any one of the first to thirteenth aspects on a substrate to form an underlayer film, on the underlayer film
- a method of forming a pattern structure for forming a self-assembled film comprising a step of applying and baking a self-assembled film-forming composition on
- a method for forming a pattern structure for forming a self-assembled film comprising a step of removing a surface layer of the lower layer film, and a step of applying and baking a self-assembled film-forming composition on the lower layer film from which the surface layer has been removed;
- the fourteenth aspect or the fifteenth aspect includes a step of forming a base film
- An eighteenth aspect is a device obtained by the pattern structure forming method according to any one of the fourteenth aspect to the seventeenth aspect.
- the underlayer film forming composition of the self-assembled film of the present invention can form an underlayer film in which the self-assembled film formed thereon can be easily arranged in a desired vertical pattern.
- the lower layer film formed by using the composition for forming the lower layer of the self-assembled film of the present invention does not cause intermixing with the self-assembled film formed on the upper layer, and forms a vertical pattern on the self-assembled film. can do.
- the underlayer film-forming composition of the present invention comprises a self-assembled film, in particular an organic polymer chain (A) containing an organic monomer (a) as a unit structure, and a monomer structure (b) different from the organic monomer (a). And a polymer film (B) formed by bonding to the organic polymer chain (A) and forming a lower layer film for a self-assembled film obtained by thermal firing. And by the lower layer film formed from the lower layer film formation composition of this invention, micro phase separation can be induced in the block polymer in such a self-assembled film, and it can make it self-assemble.
- the polymer contained in the lower layer film-forming composition of the present invention is a polymer having a unit structure of a polycyclic aromatic vinyl compound such as a vinyl naphthalene unit structure, and the lower layer film formed from the polymer is an upper layer thereof.
- the self-assembled polymer in the self-assembled film can be microphase-separated to form a self-assembled film having a vertical lamellar structure or a vertical cylinder structure.
- the self-assembled film microphase-separated by the underlayer film formed from the underlayer film-forming composition of the self-assembled film of the present invention is an organic polymer chain (A) and polymer chain (B) polymer.
- A organic polymer chain
- B polymer chain
- Various applications can be considered using the difference in properties between the two. For example, it is also possible to form a pattern corresponding to a resist pattern by using an etching rate difference (an alkali dissolution rate difference or a gas etching rate difference) between polymers.
- FIG. 1 is a scanning electron micrograph showing a state in which a self-assembled film made of a block polymer is formed on the lower film of the self-assembled film obtained from Example 1, and the self-assembled film forms a vertical lamellar structure. (Magnification is 200,000 times).
- FIG. 2 is a scanning electron micrograph showing a state in which a self-assembled film made of a block polymer is formed on the lower film of the self-assembled film obtained in Comparative Example 1, and the self-assembled film forms a horizontal lamellar structure. (Magnification is 200,000 times).
- the present invention is directed to a composition for forming an underlayer film of a self-assembled film, and more specifically, includes a polymer having a unit structure of a polycyclic aromatic vinyl compound of 0.2 mol% or more per total unit structure of the polymer.
- the present invention relates to a composition for forming a lower layer film of a self-assembled film.
- the underlayer film forming composition of the self-assembled film of the present invention contains the above polymer and preferably a solvent, can further contain a crosslinking agent, and can further contain an acid or an acid generator. And a surfactant can be contained if desired.
- the underlayer film-forming composition of the self-assembled film of the present invention is a composition for forming a film existing in the underlayer of the self-assembled film, and this underlayer film-forming composition is applied to a substrate and baked. A lower layer film is formed, and a self-assembled film-forming composition is applied thereon and dried to form a self-assembled film.
- the underlayer film forming composition of the present invention may have a solid content of 0.01 to 20% by mass, or 0.01 to 15% by mass, or 0.1 to 15% by mass. Solid content is the remaining ratio which remove
- the proportion of the polymer in the total solid content in the underlayer film forming composition of the present invention can be 60 to 100% by mass, or 70 to 99% by mass, or 70 to 99% by mass.
- the underlayer film-forming composition of the present invention is preferably a polymer having a unit structure of an aromatic vinyl compound of 20 mol% or more per total unit structure of the polymer, and a polycyclic aromatic per total unit structure of the aromatic vinyl compound.
- the aromatic vinyl compound preferably includes vinyl naphthalene, acenaphthylene, or vinyl carbazole, each of which may be substituted, and the polycyclic aromatic vinyl compound is preferably vinyl naphthalene, acenaphthylene, or vinyl carbazole.
- the polymer used in the underlayer film-forming composition of the present invention contains a polycyclic aromatic vinyl compound as an essential component, and can optionally contain an aromatic vinyl compound as a superordinate conceptual compound of this polycyclic aromatic vinyl compound.
- polycyclic aromatic vinyl compound examples include compounds such as vinyl naphthalene, vinyl anthracene, acenaphthylene, and vinyl carbazole.
- examples of other aromatic vinyl compounds include compounds such as styrene.
- the aromatic vinyl compound preferably includes optionally substituted styrene and each optionally substituted vinyl naphthalene, acenaphthylene, or vinyl carbazole.
- the polycyclic aromatic vinyl compound is vinyl naphthalene, acenaphthylene, or It can be vinyl carbazole.
- the aromatic vinyl compound is preferably an optionally substituted styrene and an optionally substituted vinyl naphthalene, acenaphthylene, or vinyl carbazole.
- the polycyclic aromatic vinyl compound is each substituted. It may be vinyl naphthalene, acenaphthylene or vinyl carbazole which may be present.
- the said aromatic vinyl compound consists only of a polycyclic aromatic vinyl compound, the said aromatic vinyl compound can be made into the vinyl naphthalene, acenaphthylene, or vinyl carbazole which may respectively be substituted.
- a polymer having a unit structure of an aromatic vinyl compound of 60 to 95 mol% based on the total unit structure of the polymer it is preferable to use a polymer having a unit structure of an aromatic vinyl compound of 60 to 95 mol% based on the total unit structure of the polymer.
- the aromatic vinyl compound and the polycyclic aromatic vinyl compound can be copolymerized to form a polymer.
- examples of the substituent of the aromatic ring include an alkyl group, a hydroxy group, a carboxyl group, and a halogen group (for example, a fluorine group, a chlorine group, a bromine group, and an iodine group). Can be mentioned.
- alkyl group examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1- Methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2 -Dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4 -Methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl
- a cyclic alkyl group can also be used as the alkyl group.
- the cyclic alkyl group having 1 to 10 carbon atoms includes a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group.
- Cyclopentyl group 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclo Propyl group, 2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3 -Ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1, -Dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group,
- the polymer may further have a unit structure having a crosslinking group as a copolymerization component.
- the polymer has a unit structure having the cross-linking group
- the polymer has a unit structure having the cross-linking group in an amount of 1 to 80 mol%, preferably 5 to 40 mol%, based on the total unit structure of the polymer. Can do.
- the cross-linking group can be a hydroxy group, an epoxy group, a protected hydroxy group, or a protected carboxyl group.
- Examples of the monomer having a unit structure having a hydroxy group include a vinyl group-containing hydroxy group derived from hydroxyalkyl (meth) acrylate, vinyl alcohol and the like, and a phenolic hydroxy group such as hydroxystyrene.
- Examples of the alkyl group include the above alkyl groups, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group.
- (meth) acrylate means both methacrylate and acrylate.
- Examples of the monomer having a unit structure having an epoxy group include a vinyl group-containing epoxy group derived from epoxy (meth) acrylate, glycidyl (meth) acrylate and the like.
- Examples of the monomer having a unit structure having a protected hydroxy group include a monomer (4-tert-butoxystyrene) obtained by protecting the hydroxy group of hydroxystyrene with a tertiary butoxy (tert-butoxy) group. Or a monomer that protects a hydroxy group by reacting a phenolic hydroxy group such as hydroxystyrene with a vinyl ether compound, or a monomer that protects a hydroxy group by reacting an alcoholic hydroxy group such as hydroxyethyl methacrylate with a vinyl ether compound. Can be mentioned.
- vinyl ether compound examples include aliphatic vinyl ethers having an alkyl chain having 1 to 10 carbon atoms and a vinyl ether group, such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, normal butyl vinyl ether, 2-ethylhexyl vinyl ether, tert-butyl vinyl ether, cyclohexyl vinyl ether and the like.
- cyclic vinyl ether compounds such as 2,3-dihydrofuran, 4-methyl-2,3-dihydrofuran and 2,3-dihydro-4H-pyran.
- Examples of the monomer having a unit structure having a protected carboxyl group include monomers having a carboxyl group protected by reacting a vinyl ether compound with a carboxyl group of (meth) acrylic acid or vinylbenzoic acid.
- Examples of the vinyl ether compound used here include the above-mentioned vinyl ether compounds.
- a vinyl compound is further included.
- the polymer may have a unit structure derived from the vinyl compound in a proportion of 1 to 80 mol%, preferably 5 to 40 mol%, based on the total unit structure of the polymer. .
- vinyl compounds include methyl (meth) acrylate, ethyl (meth) acrylate, normal hexyl (meth) acrylate, isopropyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, Anthrylmethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,2-trichloroethyl (meth) acrylate, 2-bromoethyl (meth) acrylate, 4-hydroxybutyl (meth) Acrylate, 2-methoxyethyl (meth) acrylate, butoxy (2-ethyl) (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, (meth) acrylamide, N-methyl (meth) acrylamide, -Ethyl (meth) acrylamide,
- the weight average molecular weight of the polymer used for the underlayer film forming composition of the self-assembled film of the present invention is in the range of 1,000 to 200,000, or 1,000 to 100,000, or 1,000 to 5,000. Can be used. The weight average molecular weight can be measured by GPC.
- GPC measurement conditions are, for example, GPC apparatus (trade name HLC-8220 GPC, manufactured by Tosoh Corporation), GPC columns (trade names Shodex KF803L, KF802, KF801, Showa Denko ( The column temperature is 40 ° C., the eluent (elution solvent) is tetrahydrofuran, the flow rate (flow rate) is 1.0 ml / min, and the standard sample is polystyrene (made by Showa Denko KK). .
- the underlayer film forming composition of the self-assembled film of the present invention can contain a crosslinking agent component.
- the crosslinking agent include melamine compounds, substituted urea compounds, or polymer compounds thereof.
- it is a cross-linking agent having at least two cross-linking substituents, specifically methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzogwanamine, butoxy Compounds such as methylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. Moreover, the condensate of these compounds can also be used.
- the addition amount of the crosslinking agent in the underlayer film forming composition of the self-assembled film of the present invention varies depending on the coating solvent used, the base substrate used, the required solution viscosity, the required film shape, etc.
- the content is 0.001 to 80% by mass, preferably 0.01 to 50% by mass, more preferably 0.05 to 40% by mass, based on the minute.
- These cross-linking agents may cause a cross-linking reaction by self-condensation, but when a cross-linkable substituent is present in the above-mentioned polymer of the present invention, it can cause a cross-linking reaction with those cross-linkable substituents.
- an acid or an acid generator can be included as a catalyst for promoting the crosslinking reaction, that is, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, Acidic compounds such as citric acid, benzoic acid, hydroxybenzoic acid, naphthalene carboxylic acid and / or 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic alkyl sulfonates
- Thermal acid generators such as esters can be blended. These blending amounts are 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, preferably 0.01 to 3% by mass, based on the total solid content of the underlayer film forming composition of the present invention. is there.
- Examples of the acid generator include not only the thermal acid generator but also a photoacid generator.
- the photoacid generator generates an acid upon exposure of the resist. Therefore, the acidity of the lower layer film can be adjusted. This is a method for matching the acidity of the lower layer film with the acidity of the upper layer resist. Further, the pattern shape of the resist formed in the upper layer can be adjusted by adjusting the acidity of the lower layer film.
- Examples of the photoacid generator contained in the composition for forming a lower film of a self-assembled film of the present invention include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.
- onium salt compounds include diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormalbutanesulfonate, diphenyliodonium perfluoronormaloctanesulfonate, diphenyliodonium camphorsulfonate, bis (4-tert-butylphenyl) iodonium camphor.
- Iodonium salt compounds such as sulfonate and bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, and triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfone Sulfonium salt compounds such as trifluoromethane sulfonate and the like.
- sulfonimide compounds include N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoronormalbutanesulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide and N- (trifluoromethanesulfonyloxy) naphthalimide. Can be mentioned.
- Examples of the disulfonyldiazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, and bis (2,4-dimethylbenzenesulfonyl). And diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.
- a photo-acid generator can use only 1 type, or can be used in combination of 2 or more type. When the photoacid generator is used, the proportion thereof is 0.01 to 5 parts by mass, or 0.1 to 3 parts by mass with respect to 100 parts by mass of the solid content of the lower layer film-forming composition of the present invention. Or 0.5 to 1 part by mass.
- the rheology modifier is added mainly for the purpose of improving the fluidity of the lower layer film-forming composition and improving the film thickness uniformity of the lower layer film-forming composition, particularly in the baking step.
- Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate and butyl isodecyl phthalate; adipic acid derivatives such as dinormal butyl adipate, diisobutyl adipate, diisooctyl adipate and octyl decyl adipate; Mention of maleic acid derivatives such as normal butyl maleate, diethyl maleate and dinonyl maleate; oleic acid derivatives such as methyl oleate, butyl oleate and tetrahydrofurfuryl oleate; or stearic acid derivatives such as normal butyl stearate and
- Surfactant can be mix
- the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether Polyoxyethylene alkyl allyl ethers; polyoxyethylene / polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, etc.
- Sorbitan fatty acid esters polyoxyethylene sorbitan monolaurate, polyoxyethylene sol
- Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as tan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate; EFTOP EF301, EF303, EF352 (Mitsubishi Materials Electronics Kasei Co., Ltd.
- the solvent used in producing the lower layer film-forming composition by dissolving the above-mentioned polymer and optionally the crosslinking agent component, the crosslinking catalyst, etc. includes ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol propyl ether Acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, Lohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methyl
- organic solvents are used alone or in combination of two or more.
- high boiling point solvents such as propylene glycol monobutyl ether and propylene glycol monobutyl ether acetate can be mixed and used.
- propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, butyl acetate, ethyl lactate, butyl lactate, ⁇ -butyrolactone, cyclohexanone, and the like are preferable for improving the leveling property.
- the substrate examples include a silicon wafer substrate, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a glass substrate, an ITO substrate, a polyimide substrate, and a low dielectric constant material (low-k material) coated substrate.
- the lower layer film formation composition of this invention is apply
- the firing conditions are appropriately selected from firing temperatures of 80 ° C. to 300 ° C., or 80 ° C. to 250 ° C., and firing times of 0.3 to 60 minutes.
- the firing temperature is 150 ° C. to 250 ° C.
- the firing time is 0.5 to 2 minutes.
- the thickness of the lower layer film to be formed is, for example, 10 to 1,000 nm, or 20 to 500 nm, or 10 to 300 nm, or 5 to 100 nm.
- a self-assembled film layer is formed on the obtained lower layer film.
- Formation of the self-assembled film layer can be performed by applying a solution of a self-assembled film forming composition described later onto the lower film and baking it.
- the firing temperature is appropriately selected from, for example, 80 to 140 ° C. and a firing time of 0.3 to 60 minutes.
- the firing temperature is 80 to 120 ° C. and the firing time is about 0.5 to 2 minutes.
- the film thickness of the self-assembled film is, for example, 30 to 10,000 nm, or 20 to 2,000 nm, or about 10 to 200 nm.
- the self-assembled film used in the present invention comprises an organic polymer chain (A) containing an organic monomer (a) as a unit structure, and an organic polymer chain (A) containing a monomer (b) different from the organic monomer (a) as a unit structure ( B), and a film made of a block polymer in which the organic polymer chain (B) is bonded to the organic polymer chain (A) can be used.
- the composition for forming the self-assembled film (referred to as a self-assembled film-forming composition) can contain the block polymer and an organic solvent described later. At this time, the solid content in the self-assembled film-forming composition is reduced.
- the solid content is the remaining ratio obtained by removing the solvent from the self-assembled film forming composition.
- the ratio of the block polymer in the total solid content in the self-assembled film forming composition is 30 to 100% by mass, or 50 to 100% by mass, or 50 to 90% by mass, or 50 to 80% by mass. Can do.
- the kind of block which exists in the said block polymer can be made into 2 or 3 or more.
- the number of blocks present in the block polymer can be 2 or 3 or more.
- an organic polymer chain (C) containing the monomer (c) as a unit structure can be used in the block polymer.
- examples of the block polymer include patterns of AB, ABAB, ABA, ABC and the like.
- the polymerization process consists only of an initiation reaction and a growth reaction and does not involve a side reaction that deactivates the growth terminal.
- the growth terminal can continue to maintain a growth activity reaction during the polymerization reaction. Therefore, by preventing chain transfer, an organic polymer chain (A) having a uniform length can be obtained from the monomer (a).
- the polymerization proceeds under the monomer (b), and the block polymer (AB) can be formed.
- the polymer chain (A) and the polymer chain (B) have a molar ratio of 1: 9 to 9: 1, preferably 3: 7 to 5: 5. be able to.
- the homopolymer chain A or B is a polymerizable compound having at least one reactive group capable of radical polymerization (vinyl group or vinyl group-containing organic group).
- the weight average molecular weight Mn of the block polymer used in the present invention is preferably 1,000 to 100,000, or 5,000 to 100,000. If it is less than 1,000, the applicability to the base substrate may be poor, and if it is 100,000 or more, the solubility in a solvent may be poor.
- the monomer (a) and monomer (b) forming the block polymer are respectively quaternized, for example, acrylic acid and its alkyl ester, methacrylic acid and its alkyl ester, N, N-dimethyl (meth) acrylamide.
- a block polymer having no crosslinking reaction group such as a hydroxy group, an epoxy group, a protected hydroxy group, or a protected carboxyl group, or having a crosslinking reaction group
- a crosslinking reaction group such as a hydroxy group, an epoxy group, a protected hydroxy group, or a protected carboxyl group
- polystyrene (A) and polymethyl methacrylate (B) polystyrene (A) and polyisoprene (B), or polystyrene (A) and polybutadiene (B), polystyrene (A) and poly
- a block polymer composed of each combination of dimethylsiloxane (B), polystyrene (A) and polyethylene oxide (B), polystyrene (A) and polyvinylpyridine (B) is used.
- a polystyrene / poly (methyl methacrylate) copolymer, a polystyrene / polyisoprene copolymer, or a polystyrene / polybutadiene copolymer is preferable.
- the composition for forming a self-assembled film used in the present invention includes the above-mentioned block polymer and organic solvent, and further, if necessary, a crosslinkable compound, a crosslinking catalyst, a light-absorbing compound, a surfactant, a hardness adjusting polymer compound, and an antioxidant.
- An agent, a thermal polymerization inhibitor, a surface modifier, a defoaming agent, and the like can be added.
- the self-assembled film forming composition used in the present invention further contains components such as ⁇ -diketone, colloidal silica, colloidal alumina, organic polymer, silane coupling agent, radical generator, triazene compound, and alkali compound. It may be added.
- the self-assembled film forming composition used in the present invention is usually formed by dissolving or dispersing a block polymer containing two homopolymer chains (A) and (B) in an organic solvent.
- organic solvent used here examples include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, alcohol solvents, ketone solvents, ether solvents, ester solvents, nitrogen-containing solvents, and sulfur-containing solvents. At least one selected from the group consisting of: Specifically, examples of the organic solvent include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i- Aliphatic hydrocarbon solvents such as octane, cyclohexane and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, i-propyl benzene, diethylbenzene, i-but
- propylene glycol monomethyl ether propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate and propylene glycol monopropyl ether acetate are preferred from the viewpoint of storage stability of the solution of the self-assembled film-forming composition.
- a catalyst may be used when thermosetting the self-assembled film forming composition.
- a catalyst used in this case an acid or an acid generator used when forming (curing) a lower layer film from the above-described lower layer film forming composition of the present invention can be used as a catalyst.
- a self-organized film forming composition containing a polymer not containing the block polymer, if necessary, containing the block polymer can be mixed.
- a polymer obtained by radical polymerization of the following polymerizable compound can be used as the polymer not containing the block polymer.
- the mixing ratio of the polymer not containing the block polymer in the self-assembled film-forming composition is 10 to 1,000 parts by mass, preferably 10 to 100 parts by mass with respect to 100 parts by mass of the block polymer. be able to.
- a cross-linking polymer can be used as the polymer not containing the block polymer.
- examples thereof include a polymer of a polymerizable compound such as hydroxystyrene, tris- (2-hydroxylethyl) -isocyanuric acid, and tris- (2-hydroxylethyl) -isocyanuric acid ester (meth) acrylate.
- polymerizable compounds other than the above that constitute a polymer not containing a block polymer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol.
- examples of the polymerizable compound constituting the polymer not containing the block polymer include polymerizable compounds having an ethylenically unsaturated bond, and are obtained, for example, by a reaction between a polyvalent isocyanate compound and a hydroxyalkyl unsaturated carboxylic acid ester compound.
- urethane compounds that can be obtained compounds that can be obtained by reaction of polyvalent epoxy compounds and hydroxyalkyl unsaturated carboxylic acid ester compounds, diallyl ester compounds such as diallyl phthalate, and divinyl compounds such as divinyl phthalate. it can.
- a polymerizable compound having a vinyl ether structure can also be exemplified as a polymerizable compound constituting a polymer not including a block polymer.
- a crosslinking agent can be used as an optional component.
- the crosslinking agent include a nitrogen-containing compound having a nitrogen atom substituted with a hydroxymethyl group or an alkoxymethyl group such as a methoxymethyl group, an ethoxymethyl group, a butoxymethyl group, and a hexyloxymethyl group.
- the cross-linking agent can be cross-linked with block polymers or cross-linking polymers (excluding block polymers), but if there are no cross-linking groups in the block polymer, a matrix is formed by self-crosslinking and the block polymer is fixed.
- the crosslinking agent is used in an amount of 1 to 50 parts by weight, 3 to 50 parts by weight, or 5 to 50 parts by weight, or 10 to 40 parts by weight, or 20 to 30 parts by weight with respect to 100 parts by weight of the block copolymer. Can do.
- the type and content of the crosslinking agent By changing the type and content of the crosslinking agent, the elastic modulus and the step coverage can be adjusted.
- the self-assembled film forming composition used in the present invention can contain a crosslinking catalyst capable of generating cations and radicals by thermal baking (heating) and causing a thermal polymerization reaction of the self-assembled film. .
- a crosslinking catalyst By using a crosslinking catalyst, the reaction of the crosslinking agent is promoted.
- acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonic acid, salicylic acid, camphorsulfonic acid, sulfosalicylic acid, citric acid, benzoic acid, and hydroxybenzoic acid are used. it can.
- An aromatic sulfonic acid compound can be used as the crosslinking catalyst.
- Specific examples of the aromatic sulfonic acid compound include p-toluenesulfonic acid, pyridinium-p-toluenesulfonic acid, sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, and 1-naphthalenesulfonic acid. And pyridinium-1-naphthalenesulfonic acid.
- These crosslinking catalysts can be used alone or in combination of two or more.
- the cross-linking catalyst is 0.01 to 10 parts by mass, or 0.05 to 5 parts by mass, or 0.1 to 3 parts by mass, or 0.3 to 2 parts by mass, or 0. It can be used at 5 to 1 part by mass.
- a liquid crystal is formed by applying a self-assembled film-forming composition on a processed substrate to form a coated film, and forming the self-assembled film by irradiating or thermally baking the coated film.
- Display hard disk recording material, solid-state imaging device, solar cell panel, light emitting diode, organic light emitting device, luminescent film, fluorescent film, MEMS, actuator, antireflection material, resist, resist underlayer film, resist overlayer film, or nanoimprint
- a self-assembled film used for a template (mold) can be formed.
- the lower film before forming the self-assembled film (thermosetting film), the lower film is formed by applying the above-mentioned lower film forming composition of the present invention that stores pattern information by electron beam drawing or laser irradiation. Can do.
- the lower layer film Prior to the production of the self-assembled film (thermosetting film), there are cases where the lower layer film is coated with a resist and lithography is performed, or where the resist is not coated and lithography is performed. Since the block polymer contained in the composition for forming a self-assembled film (thermosetting film) used in the present invention has a pattern-forming ability by self-assembly itself, a resist is necessarily required in order to utilize its effectiveness. Sometimes not.
- the water contact angle of the polymer in the lower layer film is the water contact angle of the organic polymer chain (A) and polymer chain (B) of the block polymer in the upper self-assembled film. It is preferable that the value is between.
- an underlayer film is formed on a substrate by applying and baking the underlayer film forming composition of the present invention, a self-assembled film is formed thereon, and a pattern is formed by the self-assembled film.
- the self-assembled film can be applied along a preset pattern guide to form a self-assembled pattern.
- the pattern guide can be formed by applying a resist, exposing and developing.
- the self-assembled film self-assembled along the pattern guide has a portion that is preferentially removed with a developer, an etching gas, etc., depending on the type of unit structure in the polymer chain constituting the self-assembled film, These unit structures can be developed and removed to reduce the width of the resist pattern (shrink) and to form sidewalls (sidewalls).
- the photoresist formed by coating is not particularly limited as long as it is sensitive to light used for exposure, and either a negative type or a positive type photoresist can be used.
- exposure is performed through a predetermined mask.
- development is performed with an alkaline developer or the like.
- the lower layer of the present invention is used.
- a film forming composition is applied to form a lower layer film.
- the lower layer film according to the lower layer film forming composition of the present invention can self-assemble the block polymer contained in the upper layer self-assembled film by containing a specific proportion of the aromatic vinyl compound as described above. Moreover, pattern information can also be input by changing the surface property of the lower layer film.
- an external stimulus such as heat, ultraviolet light, laser, or radiation is arranged at the position.
- the polymer chain (A) component and the polymer chain (B) component of the self-assembled film-forming composition using the block polymer described above are caused to irradiate with each other, causing irregularities and surface energy (hydrophilic / hydrophobic) changes. Each can be arranged at a desired position.
- An aromatic vinyl compound is used for the polymer in the lower layer film used in the present invention, and an aromatic ring (for example, a naphthalene ring or a benzene ring) bonded to the main chain is sensitively sensed by an external stimulus and changes its shape. It is considered that information can be recorded.
- an aromatic ring for example, a naphthalene ring or a benzene ring
- the self-assembled film in which the alkali dissolution rate, the solvent dissolution rate, and the gas etching rate change depending on the type of unit structure in the polymer chain of the self-assembled film is arranged at the target position.
- the resist is dissolved at the same time as the self-assembled film whose alkali dissolution rate and solvent dissolution rate change, and high contrast development is achieved. And an excellent resist pattern can be formed.
- a step of applying and baking a lower layer film-forming composition of a self-assembled film to form a lower layer film a step of bringing a solvent into contact with the lower layer film and removing a surface layer of the lower layer film, the surface
- a method for forming a pattern structure for forming a self-assembled film which includes a step of applying and baking the self-assembled film-forming composition on the lower layer film from which the layer has been removed, is also an object.
- the solvent to be brought into contact with the lower layer film the above solvent used for the lower layer film forming composition can be used.
- the surface layer of the lower layer film can be removed by contacting the solvent, and the removal of the surface layer can reduce the initial thickness of the lower layer film to 1/10 or less.
- the lower layer film can be made a thin film of 1 to 10 nm, for example.
- the pattern structure forming method of the present invention may include a step of forming a base film on the substrate before the step of applying and baking the underlayer film forming composition of the self-assembled film to form the lower layer film. it can.
- the base film an antireflection film, a hard mask, or the like can be used.
- Synthesis example 1 8.00 g of 2-vinylnaphthalene (containing 80 mol% in the whole polymer), 1.05 g of glycidyl methacrylate (containing 10 mol% in the whole polymer), 1.38 g of butoxy (2-ethyl) methacrylate (10 in the whole polymer) (Mol% contained), 2,2′-azobisisobutyronitrile (0.6 g) and cyclohexanone (38.03 g) were dissolved, and the solution was heated and stirred at 85 ° C. for about 15 hours.
- the obtained polymer corresponded to the following formula (1-1).
- the weight average molecular weight Mw measured in terms of polystyrene by GPC was 6,000.
- Synthesis example 2 12.0 g of 2-vinylnaphthalene (containing 70 mol% in the whole polymer), 2.4 g of glycidyl methacrylate (containing 15 mol% in the whole polymer), 3.2 g of butoxy (2-ethyl) methacrylate (15 in the whole polymer) (2% mol), 2,2′-azobisisobutyronitrile (0.72 g) and propylene glycol monomethyl ether acetate (35.4 g) were dissolved, and the solution was heated and stirred at 85 ° C. for about 19 hours.
- the obtained polymer corresponded to the following formula (1-2).
- the weight average molecular weight Mw measured by GPC by polystyrene conversion was 8,380.
- Synthesis example 3 20.0 g of 2-vinylnaphthalene (containing 80 mol% in the whole polymer), 4.2 g of hydroxyethyl methacrylate (containing 20 mol% in the whole polymer), 1.2 g of 2,2′-azobisisobutyronitrile, After dissolving 106.7 g of propylene glycol monomethyl ether acetate, the solution was heated and stirred at 85 ° C. for about 15 hours. The obtained polymer corresponded to the following formula (1-3). The weight average molecular weight Mw measured in terms of polystyrene by GPC was 4,150.
- Synthesis example 4 18.0 g of 2-vinylnaphthalene (containing 90 mol% in the whole polymer), 1.69 g of hydroxyethyl methacrylate (containing 10 mol% in the whole polymer), 0.98 g of 2,2′-azobisisobutyronitrile, After 48.4 g of propylene glycol monomethyl ether acetate was dissolved, the solution was heated and stirred at 85 ° C. for about 20 hours. The obtained polymer corresponded to the following formula (1-4). The weight average molecular weight Mw measured by GPC by polystyrene conversion was 8,420.
- Synthesis example 7 8.88 g of 2-vinylnaphthalene (containing 20 mol% in the whole polymer), 18.0 g of styrene (containing 60 mol% in the whole polymer), 7.51 g of hydroxyethyl methacrylate (containing 20 mol% in the whole polymer), After dissolving 1.72 g of 2,2′-azobisisobutyronitrile and 84.4 g of propylene glycol monomethyl ether acetate, the solution was heated and stirred at 85 ° C. for about 20 hours. The obtained polymer corresponded to the following formula (1-7). The weight average molecular weight Mw measured in terms of polystyrene by GPC was 8,520.
- Synthesis example 8 11.00 g of acenaphthylene (containing 80 mol% in the whole polymer), 2.32 g of hydroxyethyl methacrylate (containing 20 mol% in the whole polymer), 0.40 g of 2,2′-azobisisobutyronitrile, propylene glycol monomethyl After dissolving 32.01 g of ether acetate, the solution was heated and stirred at 85 ° C. for about 18 hours. The obtained polymer corresponded to the following formula (1-8). The weight average molecular weight Mw measured in terms of polystyrene by GPC was 8,820.
- Synthesis Example 9 11.00 g of vinyl carbazole (containing 80 mol% in the whole polymer), 1.85 g of hydroxyethyl methacrylate (containing 20 mol% in the whole polymer), 0.39 g of 2,2′-azobisisobutyronitrile, 30 cyclohexanone After dissolving 89 g, the solution was heated and stirred at 85 ° C. for about 19 hours. The obtained polymer corresponded to the following formula (1-9). The weight average molecular weight Mw measured in terms of polystyrene by GPC was 6,950.
- Example 1 To 2 g of the resin obtained in Synthesis Example 1, 0.01 g of a surfactant (manufactured by DIC Corporation, product name: Megafac [trade name] R-30, component is a fluorosurfactant), propylene glycol monomethyl ether acetate 3 .38 g, cyclohexanone 18.0 g, and ⁇ -butyrolactone 1.1 g were used as a solution. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film
- a surfactant manufactured by DIC Corporation, product name: Megafac [trade name] R-30, component is a fluorosurfactant
- Example 2 To 2 g of the resin obtained in Synthesis Example 2, 0.01 g of a surfactant (manufactured by DIC Corporation, product name: Megafac [trade name] R-30, component is a fluorosurfactant), propylene glycol monomethyl ether acetate 15 0.8 g and dissolved in 6.8 g of propylene glycol monomethyl ether to prepare a solution. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film
- a surfactant manufactured by DIC Corporation, product name: Megafac [trade name] R-30, component is a fluorosurfactant
- Example 3 To 2 g of the resin obtained in Synthesis Example 3, 0.3 g of tetramethoxymethylglycoluril, 0.03 g of pyridinium-p-toluenesulfonate, surfactant (manufactured by DIC Corporation, product name: Megafac [trade name] R- 30, component was fluorine surfactant (0.002 g), propylene glycol monomethyl ether acetate 6.8 g, propylene glycol monomethyl ether 15.8 g dissolved in solution. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film
- Example 4 To 2 g of the resin obtained in Synthesis Example 4, 0.3 g of tetramethoxymethylglycoluril, 0.03 g of pyridinium-p-toluenesulfonate, surfactant (manufactured by DIC Corporation, product name: Megafuck [trade name] R- 30, component was fluorine surfactant (0.002 g), propylene glycol monomethyl ether acetate 13.5 g, propylene glycol monomethyl ether 9.0 g was dissolved in solution. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film
- Example 5 To 2 g of the resin obtained in Synthesis Example 5, 0.3 g of tetramethoxymethylglycoluril, 0.03 g of pyridinium-p-toluenesulfonate, surfactant (manufactured by DIC Corporation, product name: Megafuck [trade name] R- 30, component was fluorine surfactant (0.002 g), propylene glycol monomethyl ether acetate 13.5 g, propylene glycol monomethyl ether 9.0 g was dissolved in solution. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film
- Example 6 To 2 g of the resin obtained in Synthesis Example 6, 0.3 g of tetramethoxymethylglycoluril, 0.03 g of pyridinium-p-toluenesulfonate, surfactant (manufactured by DIC Corporation, product name: Megafac [trade name] R- 30, component was fluorine surfactant (0.002 g), propylene glycol monomethyl ether acetate 13.5 g, propylene glycol monomethyl ether 9.0 g was dissolved in solution. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film
- Example 7 To 2 g of the resin obtained in Synthesis Example 7, 0.3 g of tetramethoxymethylglycoluril, 0.03 g of pyridinium-p-toluenesulfonate, surfactant (manufactured by DIC Corporation, product name: Megafuck [trade name] R- 30, component was fluorine surfactant (0.002 g), propylene glycol monomethyl ether acetate 13.5 g, propylene glycol monomethyl ether 9.0 g was dissolved in solution. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film
- Example 8 Dissolved in 0.37 g of the resin obtained in Synthesis Example 8 in 0.07 g of tetramethoxymethyl glycoluril, 0.01 g of pyridinium-p-toluenesulfonate, 26.6 g of propylene glycol monomethyl ether acetate, and 3.0 g of propylene glycol monomethyl ether Solution. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film
- Example 9 To 0.37 g of the resin obtained in Synthesis Example 9, 0.07 g of tetramethoxymethyl glycoluril, 0.01 g of pyridinium-p-toluenesulfonate, 8.9 g of cyclohexanone, 8.9 g of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether Dissolved in 11.8 g to prepare a solution. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film
- Example 10 A solution was prepared by dissolving 10.2 g of propylene glycol monomethyl ether acetate and 5.9 g of propylene glycol monomethyl ether in 0.2 g of the resin obtained in Synthesis Example 4. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film
- Example 11 A solution was prepared by dissolving 10.2 g of butyl acetate in 0.2 g of the resin obtained in Synthesis Example 10. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film
- Example 12 A solution was prepared by dissolving 10.2 g of butyl acetate in 0.2 g of the resin obtained in Synthesis Example 11. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film
- Comparative Example 1 A solution prepared by dissolving 0.15 g of tetramethoxymethyl glycoluril, 0.01 g of paraphenolsulfonic acid, 14.8 g of propylene glycol monomethyl ether acetate, and 31.4 g of propylene glycol monomethyl ether in 0.59 g of the resin obtained in Comparative Synthesis Example 1. It was. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film
- cresol novolac resin commercial product, weight average molecular weight is 4,000
- a solution of cresol novolac resin was baked on a silicon wafer at 205 ° C. for 1 minute using a spin coater to form an organic hard mask layer (film thickness 0.20 ⁇ m).
- CF 4 gas as an etching gas
- the dry etching rate was measured in the same manner as in Examples 1 to 9 and Comparative Example 1, and Examples 1 to 9 and Comparative Example 1 were used to dry the organic hard mask layer. Comparison was made with the etching rate.
- the results are shown in Table 2.
- the speed ratio (1) is (lower layer of self-assembled film used in Examples 1 to 9 and Comparative Example 1, fired film at 240 ° C. for 1 minute) / (cresol novolak resin, fired film at 205 ° C. for 1 minute) It is a dry etching rate ratio.
- the underlayer film forming compositions of the self-assembled films obtained in Examples 1 to 7 and Comparative Example 1 were respectively applied on a silicon wafer and heated on a hot plate at 240 ° C. for 1 minute to form a self-assembled film.
- a lower layer film (A layer) to be present in the lower layer was obtained.
- the thickness of these lower layers was 200 nm.
- the underlayer film forming composition of the self-assembled film obtained in Example 8 and Example 9 was applied onto a silicon wafer, and heated on a hot plate at 240 ° C. for 1 minute, to form a lower layer of the self-assembled film.
- the lower layer film (A layer) to be present in was obtained.
- a self-assembled film-forming composition comprising the block polymer is applied by a spinner, heated on a hot plate at 100 ° C. for 1 minute, and a 40 nm-thick self-assembled film ( B layer) was formed. Subsequently, it was heated at 240 ° C. for 5 minutes on a hot plate in a nitrogen atmosphere to induce a microphase separation structure of the block polymer.
- the lower layer films obtained from Example 1 to Example 12 are the upper layer self-assembled film, and the block polymer microphase separation structure composed of polystyrene and poly (methyl methacrylate) is formed on the substrate. It was possible to induce it vertically. In addition, the ability to induce perpendicularly to the substrate is not limited by components other than the polycyclic vinyl structure, as shown in the components contained in the lower layer films obtained from Examples 1 to 12. It was. On the other hand, as shown in the result of the lower layer film obtained from the comparative example, in the film not containing vinyl naphthalene having a polycyclic vinyl structure, the block polymer in the upper self-assembled film is perpendicular to the substrate. The result was that microphase separation could not be performed.
- Liquid crystal display recording material for hard disk, solid-state imaging device, solar cell panel, light emitting diode, organic light emitting device, luminescent film, fluorescent film, MEMS, actuator, antireflection material, resist, resist underlayer film, resist overlayer film, or nanoimprint
- a self-assembled film is used for a template for the like, but the present invention uses a polymer containing a polycyclic aromatic vinyl compound as a lower film of the self-assembled film, and in particular, a lower film containing vinylnaphthalene is blocked. It is possible to induce a polymer microphase separation structure perpendicular to the substrate.
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Abstract
Description
また非硬化性ポリスチレン/ポリ(メチルメタクリレート)コポリマーを用いたプラズマエッチングを用いたナノパターニング特性について報告されている(特許文献2)。
さらに非硬化性ポリスチレン/ポリ(メチルメタクリレート)コポリマーを用いたナノパターニング特性について報告されている(特許文献3)。 For example, the property which mixed the organic photochromic material in the non-curable polystyrene / poly (methyl methacrylate) copolymer is reported (nonpatent literature 1).
In addition, nanopatterning characteristics using plasma etching using non-curable polystyrene / poly (methyl methacrylate) copolymer have been reported (Patent Document 2).
Furthermore, nanopatterning properties using non-curable polystyrene / poly (methyl methacrylate) copolymers have been reported (Patent Document 3).
ブロックポリマーを構成する複数のセグメントを規則的に配列させてブロックポリマー層にパターンを形成するパターン形成方法が開示されている(特許文献2を参照)。
ブロックポリマー、架橋剤及び有機溶剤を含む膜形成組成物が開示されている。その膜形成組成物を用いた自己組織化膜では、ブロックポリマーをシリンダー形状にパターニングするために下層膜(例えば、有機膜を使用)にパターン情報を入力することができる。加工基板上の下層膜(例えば、有機膜を使用)にパターンを目的の位置に配列させるために紫外線、又は放射線を配列位置と重なるよう照射し、凹凸や表面エネルギー(親水・疎水性)変化を起こさせ、ブロックポリマーを用いた(自己組織化)膜形成組成物のポリマー鎖(A)成分やポリマー鎖(B)成分をそれぞれ目的の位置に配列させることができる(以上、特許文献3を参照)。 A thin film coating composition using a block polymer comprising a polymer chain having a fluorine-containing vinyl monomer unit and a polymer chain having at least a vinyl monomer unit having a silyl group is disclosed (see Patent Document 1). ).
A pattern forming method for forming a pattern in a block polymer layer by regularly arranging a plurality of segments constituting the block polymer is disclosed (see Patent Document 2).
A film-forming composition comprising a block polymer, a crosslinking agent and an organic solvent is disclosed. In the self-assembled film using the film-forming composition, pattern information can be input to the lower layer film (for example, using an organic film) in order to pattern the block polymer into a cylinder shape. Irradiate ultraviolet rays or radiation so that the pattern is arranged at the target position on the lower layer film (for example, using an organic film) on the processed substrate, and the unevenness and surface energy (hydrophilic / hydrophobic) changes. The polymer chain (A) component and the polymer chain (B) component of the (self-assembled) film-forming composition using the block polymer can be arranged at desired positions, respectively (see Patent Document 3 above) ).
第2観点として、前記ポリマーが、ポリマーの全単位構造あたり芳香族ビニル化合物の単位構造を20モル%以上有し、且つ該芳香族ビニル化合物の全単位構造あたり多環芳香族ビニル化合物の単位構造を1モル%以上有するポリマーであることを特徴とする、第1観点に記載の自己組織化膜の下層膜形成組成物、
第3観点として、前記芳香族ビニル化合物が、各々置換されていてもよいビニルナフタレン、アセナフチレン又はビニルカルバゾールを含み、且つ、前記多環芳香族ビニル化合物がビニルナフタレン、アセナフチレン又はビニルカルバゾールである、第2観点に記載の自己組織化膜の下層膜形成組成物、
第4観点として、前記芳香族ビニル化合物が、置換されていてもよいスチレンと、各々置換されていてもよいビニルナフタレン、アセナフチレン又はビニルカルバゾールとを含み、前記多環芳香族ビニル化合物がビニルナフタレン、アセナフチレン又はビニルカルバゾールである、第2観点又は第3観点に記載の自己組織化膜の下層膜形成組成物、
第5観点として、前記芳香族ビニル化合物が、置換されていてもよいスチレンと、各々置換されていてもよいビニルナフタレン、アセナフチレン又はビニルカルバゾールであり、前記多環芳香族ビニル化合物が、各々置換されていてもよいビニルナフタレン、アセナフチレン又はビニルカルバゾールである、第2観点乃至第4観点のうちいずれか1項に記載の自己組織化膜の下層膜形成組成物、
第6観点として、前記芳香族ビニル化合物が、多環芳香族ビニル化合物のみからなり、前記芳香族ビニル化合物が、各々置換されていてもよいビニルナフタレン、アセナフチレン又はビニルカルバゾールである、第2観点乃至第5観点のうちいずれか1項に記載の自己組織化膜の下層膜形成組成物、
第7観点として、前記ポリマーが、ポリマーの全単位構造あたり芳香族ビニル化合物の単位構造を60~95モル%有する、第2観点乃至第6観点のうちいずれか1項に記載の自己組織化膜の下層膜形成組成物、
第8観点として、前記ポリマーが、更に架橋形成基を有する単位構造を有する、第1観点乃至第7観点のうちいずれか1項に記載の自己組織化膜の下層膜形成組成物、
第9観点として、前記架橋形成基がヒドロキシ基、エポキシ基、保護されたヒドロキシ基又は保護されたカルボキシル基である、第8観点に記載の自己組織化膜の下層膜形成組成物、
第10観点として、更に架橋剤を含む、第1観点乃至第9観点のうちいずれか1項に記載の自己組織化膜の下層膜形成組成物、
第11観点として、更に酸又は酸発生剤を含む、第1観点乃至第10観点のいずれか1項に記載の自己組織化膜の下層膜形成組成物、
第12観点として、前記自己組織化膜が、有機モノマー(a)を単位構造として含む有機ポリマー鎖(A)と、有機モノマー(a)とは異なるモノマー(b)を単位構造として含み且つ該有機ポリマー鎖(A)に結合してなるポリマー鎖(B)とを含むブロックポリマーより成る膜である、第1観点乃至第11観点のうちいずれか1項に記載の自己組織化膜の下層膜形成組成物、
第13観点として、前記ブロックポリマーが、ポリスチレン(A)とポリメチルメタクリレート(B)、ポリスチレン(A)とポリイソプレン(B)、ポリスチレン(A)とポリブタジエン(B)、ポリスチレン(A)とポリジメチルシロキサン(B)、ポリスチレン(A)とポリエチレンオキシド(B)、又はポリスチレン(A)とポリビニルピリジン(B)の各組み合わせからなるブロックポリマーである、第12観点に記載の自己組織化膜の下層膜形成組成物、
第14観点として、基板上に第1観点乃至第13観点のうちいずれか1項に記載の自己組織化膜の下層膜形成組成物を塗布し焼成し下層膜を形成する工程、該下層膜上に自己組織化膜形成組成物を塗布し焼成する工程を含む、自己組織化膜を形成するパターン構造の形成方法、
第15観点として、基板上に第8観点又は第9観点に記載の自己組織化膜の下層膜形成組成物を塗布し焼成し下層膜を形成する工程、該下層膜に溶剤を接触させて該下層膜の表面層を除去する工程、該表面層を除去した下層膜上に自己組織化膜形成組成物を塗布し焼成する工程を含む、自己組織化膜を形成するパターン構造の形成方法、
第16観点として、自己組織化膜の下層膜形成組成物を塗布し焼成し下層膜を形成する工程の前に、基材上に下地膜を形成する工程を含む、第14観点又は第15観点に記載のパターン構造の形成方法、
第17観点として、前記下地膜が反射防止膜又はハードマスクである、第16観点に記載のパターン構造の形成方法、
第18観点として、第14観点乃至第17観点のうちいずれか1項に記載のパターン構造の形成方法により得られたデバイスである。 As a first aspect of the present invention, there is provided a composition for forming a lower film of a self-assembled film, comprising a polymer having a unit structure of a polycyclic aromatic vinyl compound of 0.2 mol% or more per total unit structure of the polymer ,
As a second aspect, the polymer has a unit structure of an aromatic vinyl compound of 20 mol% or more per total unit structure of the polymer, and a unit structure of a polycyclic aromatic vinyl compound per total unit structure of the aromatic vinyl compound A composition for forming a lower layer film of a self-assembled film according to the first aspect, characterized in that the polymer is a polymer having 1 mol% or more of
As a third aspect, the aromatic vinyl compound includes vinyl naphthalene, acenaphthylene, or vinyl carbazole, each of which may be substituted, and the polycyclic aromatic vinyl compound is vinyl naphthalene, acenaphthylene, or vinyl carbazole, The underlayer film forming composition of the self-assembled film according to 2 viewpoints,
As a fourth aspect, the aromatic vinyl compound includes optionally substituted styrene and each optionally substituted vinyl naphthalene, acenaphthylene, or vinyl carbazole, and the polycyclic aromatic vinyl compound is vinyl naphthalene, The underlayer film-forming composition for a self-assembled film according to the second aspect or the third aspect, which is acenaphthylene or vinylcarbazole,
As a fifth aspect, the aromatic vinyl compound is an optionally substituted styrene and an optionally substituted vinyl naphthalene, acenaphthylene, or vinyl carbazole, and the polycyclic aromatic vinyl compound is each substituted. The underlayer film forming composition for a self-assembled film according to any one of the second aspect to the fourth aspect, which may be vinyl naphthalene, acenaphthylene, or vinyl carbazole,
As a sixth aspect, the aromatic vinyl compound is composed only of a polycyclic aromatic vinyl compound, and the aromatic vinyl compound is vinyl naphthalene, acenaphthylene, or vinyl carbazole, each of which may be substituted. The underlayer film forming composition for a self-assembled film according to any one of the fifth aspects,
As a seventh aspect, the self-assembled film according to any one of the second to sixth aspects, wherein the polymer has a unit structure of an aromatic vinyl compound of 60 to 95 mol% per total unit structure of the polymer. An underlayer film forming composition of
As an eighth aspect, the underlayer film-forming composition for a self-assembled film according to any one of the first aspect to the seventh aspect, wherein the polymer further has a unit structure having a crosslinking group,
As a ninth aspect, the underlayer film forming composition for a self-assembled film according to the eighth aspect, in which the cross-linking group is a hydroxy group, an epoxy group, a protected hydroxy group, or a protected carboxyl group,
As a tenth aspect, the underlayer film forming composition for a self-assembled film according to any one of the first aspect to the ninth aspect, further including a crosslinking agent,
As an eleventh aspect, the underlayer film forming composition for a self-assembled film according to any one of the first aspect to the tenth aspect, further comprising an acid or an acid generator,
As a twelfth aspect, the self-assembled film includes, as a unit structure, an organic polymer chain (A) containing an organic monomer (a) as a unit structure, and a monomer (b) different from the organic monomer (a) as a unit structure. The underlayer film formation of the self-assembled film according to any one of the first aspect to the eleventh aspect, which is a film made of a block polymer including a polymer chain (B) bonded to the polymer chain (A) Composition,
As a thirteenth aspect, the block polymer contains polystyrene (A) and polymethyl methacrylate (B), polystyrene (A) and polyisoprene (B), polystyrene (A) and polybutadiene (B), polystyrene (A) and polydimethyl. The underlayer film of the self-assembled film according to the twelfth aspect, which is a block polymer composed of a combination of siloxane (B), polystyrene (A) and polyethylene oxide (B), or polystyrene (A) and polyvinylpyridine (B). Forming composition,
As a fourteenth aspect, a step of applying and baking the underlayer film forming composition of the self-assembled film according to any one of the first to thirteenth aspects on a substrate to form an underlayer film, on the underlayer film A method of forming a pattern structure for forming a self-assembled film, comprising a step of applying and baking a self-assembled film-forming composition on
As a fifteenth aspect, a step of applying and baking the underlayer film forming composition of the self-assembled film according to the eighth aspect or the ninth aspect on a substrate to form an underlayer film, contacting the underlayer film with a solvent, A method for forming a pattern structure for forming a self-assembled film, comprising a step of removing a surface layer of the lower layer film, and a step of applying and baking a self-assembled film-forming composition on the lower layer film from which the surface layer has been removed;
As a sixteenth aspect, the fourteenth aspect or the fifteenth aspect includes a step of forming a base film on a substrate before the step of applying and baking the lower layer film-forming composition of the self-assembled film to form the lower layer film. A method of forming a pattern structure according to
As a seventeenth aspect, the pattern structure forming method according to the sixteenth aspect, wherein the base film is an antireflection film or a hard mask,
An eighteenth aspect is a device obtained by the pattern structure forming method according to any one of the fourteenth aspect to the seventeenth aspect.
また本発明の自己組織化膜の下層膜形成組成物を用いて形成される下層膜は、上層に形成される自己組織化膜とのインターミキシングを引き起こさず、自己組織化膜に垂直パターンを形成することができる。 The underlayer film forming composition of the self-assembled film of the present invention can form an underlayer film in which the self-assembled film formed thereon can be easily arranged in a desired vertical pattern.
In addition, the lower layer film formed by using the composition for forming the lower layer of the self-assembled film of the present invention does not cause intermixing with the self-assembled film formed on the upper layer, and forms a vertical pattern on the self-assembled film. can do.
そして本発明の下層膜形成組成物より形成される下層膜により、このような自己組織化膜中のブロックポリマーにミクロ相分離を誘起させ、自己組織化させることができる。
特に本発明の下層膜形成組成物中に含まれるポリマーは、ビニルナフタレンの単位構造等の多環芳香族ビニル化合物の単位構造を有するポリマーであり、該ポリマーより形成される下層膜は、その上層に存在する自己組織化膜中の自己組織化ポリマーをミクロ相分離させ、垂直ラメラ構造や、垂直シリンダー構造を持った自己組織化膜を形成することができる。 The underlayer film-forming composition of the present invention comprises a self-assembled film, in particular an organic polymer chain (A) containing an organic monomer (a) as a unit structure, and a monomer structure (b) different from the organic monomer (a). And a polymer film (B) formed by bonding to the organic polymer chain (A) and forming a lower layer film for a self-assembled film obtained by thermal firing.
And by the lower layer film formed from the lower layer film formation composition of this invention, micro phase separation can be induced in the block polymer in such a self-assembled film, and it can make it self-assemble.
In particular, the polymer contained in the lower layer film-forming composition of the present invention is a polymer having a unit structure of a polycyclic aromatic vinyl compound such as a vinyl naphthalene unit structure, and the lower layer film formed from the polymer is an upper layer thereof. The self-assembled polymer in the self-assembled film can be microphase-separated to form a self-assembled film having a vertical lamellar structure or a vertical cylinder structure.
本発明の自己組織化膜の下層膜形成組成物は、上記ポリマーと好ましくは溶剤を含み、更に架橋剤を含むことができ、また更に酸又は酸発生剤を含むことができる。そして、所望により界面活性剤を含有することができる。
本発明の自己組織化膜の下層膜形成組成物は、自己組織化膜の下層に存在する膜を形成するための組成物であり、この下層膜形成組成物を基板に塗布し、焼成し、下層膜が形成され、その上に自己組織化膜形成組成物を塗布し、乾燥し、自己組織化膜が形成される。
本発明の下層膜形成組成物は、固形分を0.01~20質量%、又は0.01~15質量%、又は0.1~15質量%とすることができる。固形分とは下層膜形成組成物中から溶剤や水を除いた残りの割合である。
本発明の下層膜形成組成物における全固形分中に占める上記ポリマーの割合は、60~100質量%、又は70~99質量%、又は70~99質量%とすることができる。 The present invention is directed to a composition for forming an underlayer film of a self-assembled film, and more specifically, includes a polymer having a unit structure of a polycyclic aromatic vinyl compound of 0.2 mol% or more per total unit structure of the polymer. The present invention relates to a composition for forming a lower layer film of a self-assembled film.
The underlayer film forming composition of the self-assembled film of the present invention contains the above polymer and preferably a solvent, can further contain a crosslinking agent, and can further contain an acid or an acid generator. And a surfactant can be contained if desired.
The underlayer film-forming composition of the self-assembled film of the present invention is a composition for forming a film existing in the underlayer of the self-assembled film, and this underlayer film-forming composition is applied to a substrate and baked. A lower layer film is formed, and a self-assembled film-forming composition is applied thereon and dried to form a self-assembled film.
The underlayer film forming composition of the present invention may have a solid content of 0.01 to 20% by mass, or 0.01 to 15% by mass, or 0.1 to 15% by mass. Solid content is the remaining ratio which remove | excluded the solvent and water from the lower layer film formation composition.
The proportion of the polymer in the total solid content in the underlayer film forming composition of the present invention can be 60 to 100% by mass, or 70 to 99% by mass, or 70 to 99% by mass.
<ポリマー>
本発明の下層膜形成組成物は、好ましくはポリマーの全単位構造あたり芳香族ビニル化合物の単位構造を20モル%以上有するポリマーであって、且つ該芳香族ビニル化合物の全単位構造あたり多環芳香族ビニル化合物の単位構造を1モル%以上、又は20モル%~100モル%、又は50モル%~100モル%の範囲で有するポリマーを含む。
前記芳香族ビニル化合物は、好ましくは各々置換されていてもよいビニルナフタレン、アセナフチレン又はビニルカルバゾールを含み、前記多環芳香族ビニル化合物は、好ましくはビニルナフタレン、アセナフチレン又はビニルカルバゾールである。
本発明の下層膜形成組成物に用いられるポリマーは、多環芳香族ビニル化合物を必須として含み、この多環芳香族ビニル化合物の上位概念化合物として芳香族ビニル化合物を任意に含有することができる。 [Self-assembled film underlayer film forming composition]
<Polymer>
The underlayer film-forming composition of the present invention is preferably a polymer having a unit structure of an aromatic vinyl compound of 20 mol% or more per total unit structure of the polymer, and a polycyclic aromatic per total unit structure of the aromatic vinyl compound. A polymer having a unit structure of a group vinyl compound in the range of 1 mol% or more, or 20 mol% to 100 mol%, or 50 mol% to 100 mol%.
The aromatic vinyl compound preferably includes vinyl naphthalene, acenaphthylene, or vinyl carbazole, each of which may be substituted, and the polycyclic aromatic vinyl compound is preferably vinyl naphthalene, acenaphthylene, or vinyl carbazole.
The polymer used in the underlayer film-forming composition of the present invention contains a polycyclic aromatic vinyl compound as an essential component, and can optionally contain an aromatic vinyl compound as a superordinate conceptual compound of this polycyclic aromatic vinyl compound.
前記芳香族ビニル化合物は、好ましくは置換されていてもよいスチレンと、各々置換されていてもよいビニルナフタレン、アセナフチレン又はビニルカルバゾールとを含み、このとき多環芳香族ビニル化合物はビニルナフタレン、アセナフチレン又はビニルカルバゾールとすることができる。
そして、前記芳香族ビニル化合物は、好ましくは置換されていてもよいスチレンと、各々置換されていてもよいビニルナフタレン、アセナフチレン又はビニルカルバゾールであり、このとき多環芳香族ビニル化合物はすなわち各々置換されていてもよいビニルナフタレン、アセナフチレン又はビニルカルバゾールとすることができる。
そして、前記芳香族ビニル化合物が多環芳香族ビニル化合物のみからなる場合、前記芳香族ビニル化合物を各々置換されていてもよいビニルナフタレン、アセナフチレン又はビニルカルバゾールとすることができる。
その際、芳香族ビニル化合物の単位構造を前記ポリマーの全単位構造あたり60~95モル%有するポリマーとすることが好ましい。
上記芳香族ビニル化合物と多環芳香族ビニル化合物は共重合してポリマーとすることができる。 Examples of the polycyclic aromatic vinyl compound include compounds such as vinyl naphthalene, vinyl anthracene, acenaphthylene, and vinyl carbazole. In addition, examples of other aromatic vinyl compounds include compounds such as styrene.
The aromatic vinyl compound preferably includes optionally substituted styrene and each optionally substituted vinyl naphthalene, acenaphthylene, or vinyl carbazole. In this case, the polycyclic aromatic vinyl compound is vinyl naphthalene, acenaphthylene, or It can be vinyl carbazole.
The aromatic vinyl compound is preferably an optionally substituted styrene and an optionally substituted vinyl naphthalene, acenaphthylene, or vinyl carbazole. In this case, the polycyclic aromatic vinyl compound is each substituted. It may be vinyl naphthalene, acenaphthylene or vinyl carbazole which may be present.
And when the said aromatic vinyl compound consists only of a polycyclic aromatic vinyl compound, the said aromatic vinyl compound can be made into the vinyl naphthalene, acenaphthylene, or vinyl carbazole which may respectively be substituted.
In that case, it is preferable to use a polymer having a unit structure of an aromatic vinyl compound of 60 to 95 mol% based on the total unit structure of the polymer.
The aromatic vinyl compound and the polycyclic aromatic vinyl compound can be copolymerized to form a polymer.
上記架橋形成基はヒドロキシ基、エポキシ基、保護されたヒドロキシ基、又は保護されたカルボキシル基とすることができる。 The polymer may further have a unit structure having a crosslinking group as a copolymerization component. When the polymer has a unit structure having the cross-linking group, the polymer has a unit structure having the cross-linking group in an amount of 1 to 80 mol%, preferably 5 to 40 mol%, based on the total unit structure of the polymer. Can do.
The cross-linking group can be a hydroxy group, an epoxy group, a protected hydroxy group, or a protected carboxyl group.
これらのビニル化合物としては、メチル(メタ)アクリレート、エチル(メタ)アクリレート、ノルマルヘキシル(メタ)アクリレート、イソプロピル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェニル(メタ)アクリレート、アントリルメチル(メタ)アクリレート、2,2,2-トリフルオロエチル(メタ)アクリレート、2,2,2-トリクロロエチル(メタ)アクリレート、2-ブロモエチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、2-メトキシエチル(メタ)アクリレート、ブトキシ(2-エチル)(メタ)アクリレート、2-メチル-2-アダマンチル(メタ)アクリレート、(メタ)アクリルアミド、N-メチル(メタ)アクリルアミド、N-エチル(メタ)アクリルアミド、N-ベンジル(メタ)アクリルアミド、N-フェニル(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、N-アントリル(メタ)アクリルアミド、メチルビニルエーテル、エチルビニルエーテル、ベンジルビニルエーテル、ビニル酢酸、ビニルトリメトキシシラン、2-クロロエチルビニルエーテル、2-メトキシエチルビニルエーテル等が挙げられる。 As a polymer contained in the underlayer film forming composition of the present invention, in addition to the unit structure of the aromatic vinyl compound, the unit structure of the polycyclic aromatic vinyl compound, and the unit structure having the crosslinking group, a vinyl compound is further included. Can be used as a unit structure. When the polymer has a unit structure of the vinyl compound, the polymer may have a unit structure derived from the vinyl compound in a proportion of 1 to 80 mol%, preferably 5 to 40 mol%, based on the total unit structure of the polymer. .
These vinyl compounds include methyl (meth) acrylate, ethyl (meth) acrylate, normal hexyl (meth) acrylate, isopropyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, Anthrylmethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,2-trichloroethyl (meth) acrylate, 2-bromoethyl (meth) acrylate, 4-hydroxybutyl (meth) Acrylate, 2-methoxyethyl (meth) acrylate, butoxy (2-ethyl) (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, (meth) acrylamide, N-methyl (meth) acrylamide, -Ethyl (meth) acrylamide, N-benzyl (meth) acrylamide, N-phenyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-anthryl (meth) acrylamide, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, Examples thereof include vinyl acetic acid, vinyl trimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether and the like.
上記重量平均分子量はGPCで測定することができ、GPCの測定条件は、例えばGPC装置(商品名HLC-8220GPC、東ソー(株)製)、GPCカラム(商品名ShodexKF803L、KF802、KF801、昭和電工(株)製)、カラム温度は40℃、溶離液(溶出溶媒)はテトラヒドロフラン、流量(流速)は1.0ml/min、標準試料はポリスチレン(昭和電工(株)製)を用いて行うことができる。 The weight average molecular weight of the polymer used for the underlayer film forming composition of the self-assembled film of the present invention is in the range of 1,000 to 200,000, or 1,000 to 100,000, or 1,000 to 5,000. Can be used.
The weight average molecular weight can be measured by GPC. GPC measurement conditions are, for example, GPC apparatus (trade name HLC-8220 GPC, manufactured by Tosoh Corporation), GPC columns (trade names Shodex KF803L, KF802, KF801, Showa Denko ( The column temperature is 40 ° C., the eluent (elution solvent) is tetrahydrofuran, the flow rate (flow rate) is 1.0 ml / min, and the standard sample is polystyrene (made by Showa Denko KK). .
本発明の自己組織化膜の下層膜形成組成物は架橋剤成分を含むことができる。その架橋剤としては、メラミン系化合物、置換尿素系化合物、またはそれらのポリマー系化合物等が挙げられる。好ましくは、少なくとも2個の架橋形成置換基を有する架橋剤であり、具体的にはメトキシメチル化グリコールウリル、ブトキシメチル化グリコールウリル、メトキシメチル化メラミン、ブトキシメチル化メラミン、メトキシメチル化ベンゾグワナミン、ブトキシメチル化ベンゾグワナミン、メトキシメチル化尿素、ブトキシメチル化尿素、メトキシメチル化チオ尿素、又はメトキシメチル化チオ尿素等の化合物である。また、これらの化合物の縮合体も使用することができる。
本発明の自己組織化膜の下層膜形成組成物における架橋剤の添加量は、使用する塗布溶剤、使用する下地基板、要求される溶液粘度、要求される膜形状などにより変動するが、全固形分に対して0.001~80質量%、好ましくは 0.01~50質量%、さらに好ましくは0.05~40質量%である。
これら架橋剤は自己縮合による架橋反応を起こすこともあるが、本発明の上記のポリマー中に架橋性置換基が存在する場合は、それらの架橋性置換基と架橋反応を起こすことができる。 <Crosslinking agent component>
The underlayer film forming composition of the self-assembled film of the present invention can contain a crosslinking agent component. Examples of the crosslinking agent include melamine compounds, substituted urea compounds, or polymer compounds thereof. Preferably, it is a cross-linking agent having at least two cross-linking substituents, specifically methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzogwanamine, butoxy Compounds such as methylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. Moreover, the condensate of these compounds can also be used.
The addition amount of the crosslinking agent in the underlayer film forming composition of the self-assembled film of the present invention varies depending on the coating solvent used, the base substrate used, the required solution viscosity, the required film shape, etc. The content is 0.001 to 80% by mass, preferably 0.01 to 50% by mass, more preferably 0.05 to 40% by mass, based on the minute.
These cross-linking agents may cause a cross-linking reaction by self-condensation, but when a cross-linkable substituent is present in the above-mentioned polymer of the present invention, it can cause a cross-linking reaction with those cross-linkable substituents.
本発明では上記架橋反応を促進するための触媒としてとして酸又は酸発生剤を含むことができ、すなわち、p-トルエンスルホン酸、トリフルオロメタンスルホン酸、ピリジニウムp-トルエンスルホン酸、サリチル酸、スルホサリチル酸、クエン酸、安息香酸、ヒドロキシ安息香酸、ナフタレンカルボン酸等の酸性化合物又は/及び2,4,4,6-テトラブロモシクロヘキサジエノン、ベンゾイントシレート、2-ニトロベンジルトシレート、その他有機スルホン酸アルキルエステル等の熱酸発生剤を配合する事が出来る。これらの配合量は、本発明の下層膜形成組成物の全固形分に対して、0.0001~20質量%、好ましくは0.0005~10質量%、好ましくは0.01~3質量%である。 <Acid or acid generator>
In the present invention, an acid or an acid generator can be included as a catalyst for promoting the crosslinking reaction, that is, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, Acidic compounds such as citric acid, benzoic acid, hydroxybenzoic acid, naphthalene carboxylic acid and / or 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic alkyl sulfonates Thermal acid generators such as esters can be blended. These blending amounts are 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, preferably 0.01 to 3% by mass, based on the total solid content of the underlayer film forming composition of the present invention. is there.
光酸発生剤は、レジストの露光時に酸を生ずる。そのため、下層膜の酸性度の調整ができる。これは、下層膜の酸性度を上層のレジストとの酸性度に合わせるための一方法である。また、下層膜の酸性度の調整によって、上層に形成されるレジストのパターン形状の調整ができる。
本発明の自己組織化膜の下層膜形成組成物に含まれる光酸発生剤としては、オニウム塩化合物、スルホンイミド化合物、及びジスルホニルジアゾメタン化合物等が挙げられる。
オニウム塩化合物としてはジフェニルヨードニウムヘキサフルオロホスフエート、ジフェニルヨードニウムトリフルオロメタンスルホネート、ジフェニルヨードニウムノナフルオロノルマルブタンスルホネート、ジフェニルヨードニウムパーフルオロノルマルオクタンスルホネート、ジフェニルヨードニウムカンファースルホネート、ビス(4-tert-ブチルフェニル)ヨードニウムカンファースルホネート及びビス(4-tert-ブチルフェニル)ヨードニウムトリフルオロメタンスルホネート等のヨードニウム塩化合物、及びトリフェニルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムノナフルオロノルマルブタンスルホネート、トリフェニルスルホニウムカンファースルホネート及びトリフェニルスルホニウムトリフルオロメタンスルホネート等のスルホニウム塩化合物等が挙げられる。
スルホンイミド化合物としては、例えばN-(トリフルオロメタンスルホニルオキシ)スクシンイミド、N-(ノナフルオロノルマルブタンスルホニルオキシ)スクシンイミド、N-(カンファースルホニルオキシ)スクシンイミド及びN-(トリフルオロメタンスルホニルオキシ)ナフタルイミド等が挙げられる。
ジスルホニルジアゾメタン化合物としては、例えば、ビス(トリフルオロメチルスルホニル)ジアゾメタン、ビス(シクロヘキシルスルホニル)ジアゾメタン、ビス(フェニルスルホニル)ジアゾメタン、ビス(p-トルエンスルホニル)ジアゾメタン、ビス(2,4-ジメチルベンゼンスルホニル)ジアゾメタン、及びメチルスルホニル-p-トルエンスルホニルジアゾメタン等が挙げられる。
光酸発生剤は一種のみを使用することができ、または二種以上を組み合わせて使用することができる。
光酸発生剤が使用される場合、その割合としては、本発明の下層膜形成組成物の固形分100質量部に対して、0.01~5質量部、または0.1~3質量部、または0.5~1質量部である。 Examples of the acid generator include not only the thermal acid generator but also a photoacid generator.
The photoacid generator generates an acid upon exposure of the resist. Therefore, the acidity of the lower layer film can be adjusted. This is a method for matching the acidity of the lower layer film with the acidity of the upper layer resist. Further, the pattern shape of the resist formed in the upper layer can be adjusted by adjusting the acidity of the lower layer film.
Examples of the photoacid generator contained in the composition for forming a lower film of a self-assembled film of the present invention include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.
Examples of onium salt compounds include diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormalbutanesulfonate, diphenyliodonium perfluoronormaloctanesulfonate, diphenyliodonium camphorsulfonate, bis (4-tert-butylphenyl) iodonium camphor. Iodonium salt compounds such as sulfonate and bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, and triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfone Sulfonium salt compounds such as trifluoromethane sulfonate and the like.
Examples of the sulfonimide compounds include N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoronormalbutanesulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide and N- (trifluoromethanesulfonyloxy) naphthalimide. Can be mentioned.
Examples of the disulfonyldiazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, and bis (2,4-dimethylbenzenesulfonyl). And diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.
A photo-acid generator can use only 1 type, or can be used in combination of 2 or more type.
When the photoacid generator is used, the proportion thereof is 0.01 to 5 parts by mass, or 0.1 to 3 parts by mass with respect to 100 parts by mass of the solid content of the lower layer film-forming composition of the present invention. Or 0.5 to 1 part by mass.
本発明の下層膜形成組成物には、上記成分以外に必要に応じて更なるレオロジー調整剤、接着補助剤、界面活性剤などを添加することができる。 <Other additives>
In addition to the above components, further rheology modifiers, adhesion assistants, surfactants and the like can be added to the underlayer film forming composition of the present invention as necessary.
これらのレオロジー調整剤は、本発明の下層膜形成組成物の全固形分に対して通常30質量%未満の割合で配合される。 The rheology modifier is added mainly for the purpose of improving the fluidity of the lower layer film-forming composition and improving the film thickness uniformity of the lower layer film-forming composition, particularly in the baking step. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate and butyl isodecyl phthalate; adipic acid derivatives such as dinormal butyl adipate, diisobutyl adipate, diisooctyl adipate and octyl decyl adipate; Mention of maleic acid derivatives such as normal butyl maleate, diethyl maleate and dinonyl maleate; oleic acid derivatives such as methyl oleate, butyl oleate and tetrahydrofurfuryl oleate; or stearic acid derivatives such as normal butyl stearate and glyceryl stearate Can do.
These rheology modifiers are usually blended in a proportion of less than 30% by mass with respect to the total solid content of the underlayer film forming composition of the present invention.
これらの界面活性剤の配合量は、本発明の下層膜形成組成物の全固形分に対して通常2.0質量%以下、好ましくは1.0質量%以下である。これらの界面活性剤は単独で添加してもよいし、また2種以上の組合せで添加することもできる。 Surfactant can be mix | blended in order to suppress generation | occurrence | production of the pinhole of a lower layer film formation composition, a setup, etc., and to further improve the applicability | paintability with respect to surface unevenness. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether Polyoxyethylene alkyl allyl ethers; polyoxyethylene / polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, etc. Sorbitan fatty acid esters; polyoxyethylene sorbitan monolaurate, polyoxyethylene sol Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as tan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate; EFTOP EF301, EF303, EF352 (Mitsubishi Materials Electronics Kasei Co., Ltd. (formerly Tochem Products Co., Ltd., trade name), MegaFuck F171, F173, R-30 (DIC Corporation, trade name), Florad FC430, FC431 (Sumitomo) Fluorosurfactants such as Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (trade name, manufactured by Asahi Glass Co., Ltd.); Nporima KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
The blending amount of these surfactants is usually 2.0% by mass or less, preferably 1.0% by mass or less, based on the total solid content of the lower layer film-forming composition of the present invention. These surfactants may be added alone or in combination of two or more.
本発明の下層膜形成組成物において、上記のポリマー及び所望により架橋剤成分、架橋触媒等を溶解させ下層膜形成組成物を製造する際に用いる溶剤としては、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテル、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート、トルエン、キシレン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、2-ヒドロキシプロピオン酸エチル、2ーヒドロキシ-2-メチルプロピオン酸エチル、エトシキ酢酸エチル、ヒドロキシ酢酸エチル、2-ヒドロキシ-3-メチルブタン酸メチル、3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸エチル、3-エトキシプロピオン酸メチル、ピルビン酸メチル、ピルビン酸エチル、酢酸エチル、酢酸ブチル、乳酸エチル、乳酸ブチル、γ-ブチロラクトン等を用いることができる。これらの有機溶剤は単独で、または2種以上の組合せで使用される。
さらに、プロピレングリコールモノブチルエーテル、プロピレングリコールモノブチルエーテルアセテート等の高沸点溶剤を混合して使用することができる。
これらの溶剤の中でも、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、酢酸ブチル、乳酸エチル、乳酸ブチル、γ-ブチロラクトン及びシクロヘキサノン等がレベリング性の向上に対して好ましい。 <Solvent>
In the lower layer film-forming composition of the present invention, the solvent used in producing the lower layer film-forming composition by dissolving the above-mentioned polymer and optionally the crosslinking agent component, the crosslinking catalyst, etc. includes ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol propyl ether Acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, Lohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate Ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, γ-butyrolactone and the like can be used. These organic solvents are used alone or in combination of two or more.
Furthermore, high boiling point solvents such as propylene glycol monobutyl ether and propylene glycol monobutyl ether acetate can be mixed and used.
Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, butyl acetate, ethyl lactate, butyl lactate, γ-butyrolactone, cyclohexanone, and the like are preferable for improving the leveling property.
以下、本発明の自己組織化膜の下層膜形成組成物の使用について説明する。
基板上に上記の自己組織化膜の下層膜形成組成物を塗布し焼成し下層膜を形成する工程、該下層膜上に後述する自己組織化膜形成組成物を塗布し焼成する工程を経て、自己組織化膜を形成するパターン構造(ミクロ相分離構造ともいう)が形成される。 [Method of forming pattern structure]
Hereinafter, the use of the underlayer film forming composition of the self-assembled film of the present invention will be described.
Applying and baking the lower layer film-forming composition of the above self-assembled film on the substrate to form a lower film, and applying and baking the self-assembled film-forming composition described later on the lower film, A pattern structure (also referred to as a microphase separation structure) that forms a self-assembled film is formed.
この基盤上に、スピナー、コーター等の適当な塗布方法により本発明の下層膜形成組成物を塗布し、その後、焼成することにより下層膜を形成する。
焼成する条件としては、焼成温度80℃~300℃、又は80℃~250℃、焼成時間0.3~60分間の中から適宜、選択される。好ましくは、焼成温度150℃~250℃、焼成時間0.5~2分間である。
ここで、形成される下層膜の膜厚としては、例えば、10~1,000nmであり、または20~500nmであり、または10~300nmであり、または5~100nmである。 Examples of the substrate include a silicon wafer substrate, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a glass substrate, an ITO substrate, a polyimide substrate, and a low dielectric constant material (low-k material) coated substrate.
On this base | substrate, the lower layer film formation composition of this invention is apply | coated by suitable coating methods, such as a spinner and a coater, and a lower layer film is formed by baking after that.
The firing conditions are appropriately selected from firing temperatures of 80 ° C. to 300 ° C., or 80 ° C. to 250 ° C., and firing times of 0.3 to 60 minutes. Preferably, the firing temperature is 150 ° C. to 250 ° C., and the firing time is 0.5 to 2 minutes.
Here, the thickness of the lower layer film to be formed is, for example, 10 to 1,000 nm, or 20 to 500 nm, or 10 to 300 nm, or 5 to 100 nm.
焼成温度は例えば80~140℃で、焼成時間0.3~60分間の中から適宜、選択される。好ましくは、焼成温度80~120℃、焼成時間0.5~2分間程度である。
自己組織化膜の膜厚としては例えば30~10,000nmであり、または20~2,000nmであり、または10~200nm程度である。 Next, for example, a self-assembled film layer is formed on the obtained lower layer film. Formation of the self-assembled film layer can be performed by applying a solution of a self-assembled film forming composition described later onto the lower film and baking it.
The firing temperature is appropriately selected from, for example, 80 to 140 ° C. and a firing time of 0.3 to 60 minutes. Preferably, the firing temperature is 80 to 120 ° C. and the firing time is about 0.5 to 2 minutes.
The film thickness of the self-assembled film is, for example, 30 to 10,000 nm, or 20 to 2,000 nm, or about 10 to 200 nm.
本発明に用いられる自己組織化膜は、有機モノマー(a)を単位構造として含む有機ポリマー鎖(A)と、有機モノマー(a)とは異なるモノマー(b)を単位構造として含む有機ポリマー鎖(B)とを含み、且つ該有機ポリマー鎖(B)が該有機ポリマー鎖(A)に結合してなるブロックポリマーより成る膜を用いることができる。
上記自己組織化膜を形成するための組成物(自己組織化膜形成組成物と称する)は前記ブロックポリマーと後述する有機溶剤とを含み得、このとき自己組織化膜形成組成物における固形分を0.1~70質量%、又は0.1~50質量%、又は0.1~30質量%とすることができる。固形分とは自己組織化膜形成組成物中から溶剤を除いた残りの割合である。
自己組織化膜形成組成物における全固形分中に占める前記ブロックポリマーの割合は、30~100質量%、又は50~100質量%、又は50~90質量%、又は50~80質量%にすることができる。 <Self-assembled film and self-assembled film-forming composition>
The self-assembled film used in the present invention comprises an organic polymer chain (A) containing an organic monomer (a) as a unit structure, and an organic polymer chain (A) containing a monomer (b) different from the organic monomer (a) as a unit structure ( B), and a film made of a block polymer in which the organic polymer chain (B) is bonded to the organic polymer chain (A) can be used.
The composition for forming the self-assembled film (referred to as a self-assembled film-forming composition) can contain the block polymer and an organic solvent described later. At this time, the solid content in the self-assembled film-forming composition is reduced. It can be 0.1 to 70% by mass, or 0.1 to 50% by mass, or 0.1 to 30% by mass. The solid content is the remaining ratio obtained by removing the solvent from the self-assembled film forming composition.
The ratio of the block polymer in the total solid content in the self-assembled film forming composition is 30 to 100% by mass, or 50 to 100% by mass, or 50 to 90% by mass, or 50 to 80% by mass. Can do.
また前記有機ポリマー鎖(B)を変えることにより、例えばモノマー(c)を単位構造として含む有機ポリマー鎖(C)を前記ブロックポリマー中に用いることが可能である。
従ってブロックポリマーとしてはAB、ABAB、ABA、ABC等のパターンが挙げられる。 The kind of block which exists in the said block polymer can be made into 2 or 3 or more. The number of blocks present in the block polymer can be 2 or 3 or more.
Further, by changing the organic polymer chain (B), for example, an organic polymer chain (C) containing the monomer (c) as a unit structure can be used in the block polymer.
Accordingly, examples of the block polymer include patterns of AB, ABAB, ABA, ABC and the like.
次に有機このポリマー鎖(A)の成長末端を利用して、モノマー(a)とは異なるモノマー(b)を添加することにより、このモノマー(b)のもとで重合が進行し、ブロックポリマー(AB)を形成することができる。
例えばブロックの種類がAとBの2種類である場合に、ポリマー鎖(A)とポリマー鎖(B)はモル比で1:9~9:1、好ましくは3:7~5:5とすることができる。
ここでホモポリマー鎖A又はBは、ラジカル重合可能な反応性基(ビニル基又はビニル基含有有機基)を少なくとも一つ有する重合性化合物である。 As one of the methods for synthesizing the block polymer, it is preferable to use living radical polymerization or living cation polymerization in which the polymerization process consists only of an initiation reaction and a growth reaction and does not involve a side reaction that deactivates the growth terminal. In these polymerization reactions, the growth terminal can continue to maintain a growth activity reaction during the polymerization reaction. Therefore, by preventing chain transfer, an organic polymer chain (A) having a uniform length can be obtained from the monomer (a).
Next, by using the growth terminal of the polymer chain (A), by adding a monomer (b) different from the monomer (a), the polymerization proceeds under the monomer (b), and the block polymer (AB) can be formed.
For example, when there are two types of blocks, A and B, the polymer chain (A) and the polymer chain (B) have a molar ratio of 1: 9 to 9: 1, preferably 3: 7 to 5: 5. be able to.
Here, the homopolymer chain A or B is a polymerizable compound having at least one reactive group capable of radical polymerization (vinyl group or vinyl group-containing organic group).
中でも、ポリスチレン/ポリ(メチルメタクリレート)コポリマー、ポリスチレン/ポリイソプレンコポリマー、又はポリスチレン/ポリブタジエンコポリマーが好ましい。 In the self-assembled film forming composition used in the present invention, a block polymer having no crosslinking reaction group such as a hydroxy group, an epoxy group, a protected hydroxy group, or a protected carboxyl group, or having a crosslinking reaction group Specifically, for example, polystyrene (A) and polymethyl methacrylate (B), polystyrene (A) and polyisoprene (B), or polystyrene (A) and polybutadiene (B), polystyrene (A) and poly A block polymer composed of each combination of dimethylsiloxane (B), polystyrene (A) and polyethylene oxide (B), polystyrene (A) and polyvinylpyridine (B) is used.
Among them, a polystyrene / poly (methyl methacrylate) copolymer, a polystyrene / polyisoprene copolymer, or a polystyrene / polybutadiene copolymer is preferable.
また本発明に用いられる自己組織化膜形成組成物には、さらにβ-ジケトン、コロイド状シリカ、コロイド状アルミナ、有機ポリマー、シランカップリング剤、ラジカル発生剤、トリアゼン化合物、アルカリ化合物などの成分を添加してもよい。 The composition for forming a self-assembled film used in the present invention includes the above-mentioned block polymer and organic solvent, and further, if necessary, a crosslinkable compound, a crosslinking catalyst, a light-absorbing compound, a surfactant, a hardness adjusting polymer compound, and an antioxidant. An agent, a thermal polymerization inhibitor, a surface modifier, a defoaming agent, and the like can be added.
The self-assembled film forming composition used in the present invention further contains components such as β-diketone, colloidal silica, colloidal alumina, organic polymer, silane coupling agent, radical generator, triazene compound, and alkali compound. It may be added.
具体的には、有機溶剤としては、例えばn-ペンタン、i-ペンタン、n-ヘキサン、i-ヘキサン、n-ヘプタン、i-ヘプタン、2,2,4-トリメチルペンタン、n-オクタン、i-オクタン、シクロヘキサン、メチルシクロヘキサン等の脂肪族炭化水素系溶剤;ベンゼン、トルエン、キシレン、エチルベンゼン、トリメチルベンゼン、メチルエチルベンゼン、n-プロピルベンセン、i-プロピルベンセン、ジエチルベンゼン、i-ブチルベンゼン、トリエチルベンゼン、ジ-i-プロピルベンセン、n-アミルナフタレン、トリメチルベンゼン等の芳香族炭化水素系溶剤;メタノール、エタノール、n-プロパノール、i-プロパノール、n-ブタノール、i-ブタノール、sec-ブタノール、t-ブタノール、n-ペンタノール、i-ペンタノール、2-メチルブタノール、sec-ペンタノール、t-ペンタノール、3-メトキシブタノール、n-ヘキサノール、2-メチルペンタノール、sec-ヘキサノール、2-エチルブタノール、sec-ヘプタノール、ヘプタノール-3、n-オクタノール、2-エチルヘキサノール、sec-オクタノール、n-ノニルアルコール、2,6-ジメチル-4-ヘプタノール、n-デカノール、sec-ウンデシルアルコール、トリメチルノニルアルコール、sec-テトラデシルアルコール、sec-ヘプタデシルアルコール、フェノール、シクロヘキサノール、メチルシクロヘキサノール、3,3,5-トリメチルシクロヘキサノール、ベンジルアルコール、フェニルメチルカルビノール、ジアセトンアルコール、クレゾール等のモノアルコール系溶剤;エチレングリコール、プロピレングリコール、1,3-ブチレングリコール、2,4-ペンタンジオール、2-メチルペンタン-2,4-ジオール、2,5-ヘキサンジオール、2,4-ヘプタンジオール、2-エチルヘキサン-1,3-ジオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、トリプロピレングリコール、グリセリン等の多価アルコール系溶剤;アセトン、メチルエチルケトン、メチル-n-プロピルケトン、メチル-n-ブチルケトン、ジエチルケトン、メチル-i-ブチルケトン、メチル-n-ペンチルケトン、エチル-n-ブチルケトン、メチル-n-ヘキシルケトン、ジ-i-ブチルケトン、トリメチルノナノン、シクロヘキサノン、メチルシクロヘキサノン、2,4-ペンタンジオン、アセトニルアセトン、ジアセトンアルコール、アセトフェノン、フェンチョン等のケトン系溶剤;エチルエーテル、i-プロピルエーテル、n-ブチルエーテル、n-ヘキシルエーテル、2-エチルヘキシルエーテル、エチレンオキシド、1,2-プロピレンオキシド、ジオキソラン、4-メチルジオキソラン、ジオキサン、ジメチルジオキサン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールモノ-n-ブチルエーテル、エチレングリコールモノ-n-ヘキシルエーテル、エチレングリコールモノフェニルエーテル、エチレングリコールモノ-2-エチルブチルエーテル、エチレングリコールジブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールモノ-n-ブチルエーテル、ジエチレングリコールジ-n-ブチルエーテル、ジエチレングリコールモノ-n-ヘキシルエーテル、エトキシトリグリコール、テトラエチレングリコールジ-n-ブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノブチルエーテル、トリプロピレングリコールモノメチルエーテル、テトラヒドロフラン、2-メチルテトラヒドロフラン等のエーテル系溶剤;ジエチルカーボネート、酢酸メチル、酢酸エチル、γ-ブチロラクトン、γ-バレロラクトン、酢酸n-プロピル、酢酸i-プロピル、酢酸n-ブチル、酢酸i-ブチル、酢酸sec-ブチル、酢酸n-ペンチル、酢酸sec-ペンチル、酢酸3-メトキシブチル、酢酸メチルペンチル、酢酸2-エチルブチル、酢酸2-エチルヘキシル、酢酸ベンジル、酢酸シクロヘキシル、酢酸メチルシクロヘキシル、酢酸n-ノニル、アセト酢酸メチル、アセト酢酸エチル、酢酸エチレングリコールモノメチルエーテル、酢酸エチレングリコールモノエチルエーテル、酢酸ジエチレングリコールモノメチルエーテル、酢酸ジエチレングリコールモノエチルエーテル、酢酸ジエチレングリコールモノ-n-ブチルエーテル、酢酸プロピレングリコールモノメチルエーテル、酢酸プロピレングリコールモノエチルエーテル、酢酸プロピレングリコールモノプロピルエーテル、酢酸プロピレングリコールモノブチルエーテル、酢酸ジプロピレングリコールモノメチルエーテル、酢酸ジプロピレングリコールモノエチルエーテル、ジ酢酸グリコール、酢酸メトキシトリグリコール、プロピオン酸エチル、プロピオン酸n-ブチル、プロピオン酸i-アミル、シュウ酸ジエチル、シュウ酸ジ-n-ブチル、乳酸メチル、乳酸エチル、乳酸n-ブチル、乳酸n-アミル、マロン酸ジエチル、フタル酸ジメチル、フタル酸ジエチル等のエステル系溶剤;N-メチルホルムアミド、N,N-ジメチルホルムアミド、N,N-ジエチルホルムアミド、アセトアミド、N-メチルアセトアミド、N,N-ジメチルアセトアミド、N-メチルプロピオンアミド、N-メチル-2-ピロリドン等の含窒素系溶剤;硫化ジメチル、硫化ジエチル、チオフェン、テトラヒドロチオフェン、ジメチルスルホキシド、スルホラン、1,3-プロパンスルトン等の含硫黄系溶剤等を挙げることができる。 Examples of the organic solvent used here include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, alcohol solvents, ketone solvents, ether solvents, ester solvents, nitrogen-containing solvents, and sulfur-containing solvents. At least one selected from the group consisting of:
Specifically, examples of the organic solvent include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i- Aliphatic hydrocarbon solvents such as octane, cyclohexane and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, i-propyl benzene, diethylbenzene, i-butylbenzene, triethylbenzene, di Aromatic hydrocarbon solvents such as i-propyl benzene, n-amyl naphthalene and trimethylbenzene; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-Pentanol I-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol -3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol , Sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, Monoalcohol solvents such as sol; ethylene glycol, propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methylpentane-2,4-diol, 2,5-hexanediol, 2,4- Polyhydric alcohol solvents such as heptanediol, 2-ethylhexane-1,3-diol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin; acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl- n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methyl Ketone solvents such as lohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, fenchon; ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n- Hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibuty Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether Ether solvents such as tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n -Butyl, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, acetic acid Methylcyclohexyl, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diacetate Tylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene acetate Glycol monoethyl ether, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, nactyl lactate Ester solvents such as butyl, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate; N-methylformamide, N Nitrogen-containing solvents such as N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methyl-2-pyrrolidone; Examples thereof include sulfur-containing solvents such as diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone.
また、自己組織化膜形成組成物におけるブロックポリマーを含まないポリマーの混合割合は、ブロックポリマー100質量部に対して10~1,000質量部、好ましくは10~100質量部の割合にて混合することができる。 Furthermore, in order to improve adhesion, wettability to the base substrate, flexibility, flatness, etc., a self-organized film forming composition containing a polymer not containing the block polymer, if necessary, containing the block polymer Can be mixed. As the polymer not containing the block polymer, a polymer obtained by radical polymerization of the following polymerizable compound can be used.
The mixing ratio of the polymer not containing the block polymer in the self-assembled film-forming composition is 10 to 1,000 parts by mass, preferably 10 to 100 parts by mass with respect to 100 parts by mass of the block polymer. be able to.
前記架橋剤としては、ヒドロキシメチル基、又はメトキシメチル基、エトキシメチル基、ブトキシメチル基、及びヘキシルオキシメチル基等のアルコキシメチル基で置換された窒素原子を有する含窒素化合物が挙げられる。架橋剤はブロックポリマーや、(ブロックポリマーを含まない)架橋形成ポリマーと架橋形成が可能であるが、ブロックポリマーに架橋形成基が存在しない場合には自己架橋によりマトリックスを形成し、ブロックポリマーを固定化することができる。
前記架橋剤は、ブロックコポリマー100質量部に対して1~50質量部、または3~50質量部、または5~50質量部、または10~40質量部、または20~30質量部で使用することができる。架橋剤の種類や含有量を変えることによって、弾性率や段差被覆性を調整することができる。 In the self-assembled film forming composition used in the present invention, a crosslinking agent can be used as an optional component.
Examples of the crosslinking agent include a nitrogen-containing compound having a nitrogen atom substituted with a hydroxymethyl group or an alkoxymethyl group such as a methoxymethyl group, an ethoxymethyl group, a butoxymethyl group, and a hexyloxymethyl group. The cross-linking agent can be cross-linked with block polymers or cross-linking polymers (excluding block polymers), but if there are no cross-linking groups in the block polymer, a matrix is formed by self-crosslinking and the block polymer is fixed. Can be
The crosslinking agent is used in an amount of 1 to 50 parts by weight, 3 to 50 parts by weight, or 5 to 50 parts by weight, or 10 to 40 parts by weight, or 20 to 30 parts by weight with respect to 100 parts by weight of the block copolymer. Can do. By changing the type and content of the crosslinking agent, the elastic modulus and the step coverage can be adjusted.
前記架橋触媒としては、p-トルエンスルホン酸、トリフルオロメタンスルホン酸、ピリジニウム-p-トルエンスルホン酸、サリチル酸、カンファースルホン酸、スルホサリチル酸、クエン酸、安息香酸、及びヒドロキシ安息香酸等の酸化合物が使用できる。
また前記架橋触媒としては、芳香族スルホン酸化合物が使用できる。芳香族スルホン酸化合物の具体例としては、p-トルエンスルホン酸、ピリジニウム-p-トルエンスルホン酸、スルホサリチル酸、4-クロロベンゼンスルホン酸、4-ヒドロキシベンゼンスルホン酸、ベンゼンジスルホン酸、1-ナフタレンスルホン酸、及びピリジニウム-1-ナフタレンスルホン酸等を挙げることができる。
これら架橋触媒は、一種のみを使用することができ、また、二種以上を組み合わせて用いることもできる。
前記架橋触媒はブロックポリマー100質量部に対して0.01~10質量部、または0.05~5質量部、または0.1~3質量部、または0.3~2質量部、または0.5~1質量部で使用することができる。 Furthermore, the self-assembled film forming composition used in the present invention can contain a crosslinking catalyst capable of generating cations and radicals by thermal baking (heating) and causing a thermal polymerization reaction of the self-assembled film. . By using a crosslinking catalyst, the reaction of the crosslinking agent is promoted.
As the crosslinking catalyst, acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonic acid, salicylic acid, camphorsulfonic acid, sulfosalicylic acid, citric acid, benzoic acid, and hydroxybenzoic acid are used. it can.
An aromatic sulfonic acid compound can be used as the crosslinking catalyst. Specific examples of the aromatic sulfonic acid compound include p-toluenesulfonic acid, pyridinium-p-toluenesulfonic acid, sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, and 1-naphthalenesulfonic acid. And pyridinium-1-naphthalenesulfonic acid.
These crosslinking catalysts can be used alone or in combination of two or more.
The cross-linking catalyst is 0.01 to 10 parts by mass, or 0.05 to 5 parts by mass, or 0.1 to 3 parts by mass, or 0.3 to 2 parts by mass, or 0. It can be used at 5 to 1 part by mass.
半導体、液晶ディスプレイ、ハードディスク用記録材料、固体撮像素子、太陽電池パネル、発光ダイオード、有機発光デバイス、ルミネセントフィルム、蛍光フィルム、MEMS、アクチュエーター、反射防止材料、レジスト、レジスト下層膜、レジスト上層膜、又はナノインプリント用テンプレート(モールド)の製造に使用される加工基板(例えば、シリコン/二酸化シリコン被覆基板、シリコンウエハ基板、シリコンナイトライド基板、ガラス基板、ITO基板、ポリイミド基板、低誘電率材料(low-k材料)被覆基板等)の上に、電子線やレーザ照射による凹凸変化や表面エネルギー変化によるパターン情報を入れる本願の下層膜(Brush Layer、Migaku・Layer)形成組成物を適用することができる。そして、その上に、スピナー、コーター、スプレー、インクジェット等の適当な塗布方法により自己組織化膜形成組成物が塗布され塗布膜が形成される。 Hereinafter, an example of the use of the present invention will be described.
Semiconductors, liquid crystal displays, recording materials for hard disks, solid-state imaging devices, solar cell panels, light emitting diodes, organic light emitting devices, luminescent films, fluorescent films, MEMS, actuators, antireflection materials, resists, resist underlayer films, resist upper layer films, Or processed substrates used in the manufacture of nanoimprint templates (molds) (eg, silicon / silicon dioxide coated substrates, silicon wafer substrates, silicon nitride substrates, glass substrates, ITO substrates, polyimide substrates, low dielectric constant materials (low- The composition for forming an underlayer film (Brush Layer, Migaku Layer) of the present application in which pattern information due to unevenness or surface energy change caused by electron beam or laser irradiation is applied on a k material) a coated substrate or the like) can be applied. Then, the self-assembled film-forming composition is applied thereon by an appropriate application method such as a spinner, coater, spray, ink jet or the like to form a coating film.
フォトレジスト塗布後、所定のマスクを通して露光が行なわれる。次いで、アルカリ性現像液等によって現像が行なわれる。 The photoresist formed by coating is not particularly limited as long as it is sensitive to light used for exposure, and either a negative type or a positive type photoresist can be used.
After applying the photoresist, exposure is performed through a predetermined mask. Next, development is performed with an alkaline developer or the like.
そして、上記下層膜形成後に、アルカリ溶解速度や溶媒溶解速度やガスエッチング速度が自己組織化膜のポリマー鎖中の単位構造の種類で変化する自己組織化膜を目的の位置に配列させ、レジストを成膜し、レジストに紫外線、又は放射線を配列位置と重なるよう照射し、現像することにより、アルカリ溶解速度や溶媒溶解速度が変化する自己組織化膜と同時にレジストを溶解され、高コントラストの現像ができ、優れたレジストパターンを形成することができる。 An aromatic vinyl compound is used for the polymer in the lower layer film used in the present invention, and an aromatic ring (for example, a naphthalene ring or a benzene ring) bonded to the main chain is sensitively sensed by an external stimulus and changes its shape. It is considered that information can be recorded.
Then, after the formation of the lower layer film, the self-assembled film in which the alkali dissolution rate, the solvent dissolution rate, and the gas etching rate change depending on the type of unit structure in the polymer chain of the self-assembled film is arranged at the target position, By forming a film, irradiating the resist with ultraviolet rays or radiation so that it overlaps the alignment position, and developing, the resist is dissolved at the same time as the self-assembled film whose alkali dissolution rate and solvent dissolution rate change, and high contrast development is achieved. And an excellent resist pattern can be formed.
ここで下層膜に接触させる溶剤としては、下層膜形成組成物に用いる上記溶剤を用いることができる。溶剤を接触させることによって下層膜の表面層を除去することができ、表面層の除去は当初の下層膜の膜厚を1/10以下にすることができる。この工程により、下層膜は例えば1~10nmの薄膜とすることができる。 Therefore, in the present invention, a step of applying and baking a lower layer film-forming composition of a self-assembled film to form a lower layer film, a step of bringing a solvent into contact with the lower layer film and removing a surface layer of the lower layer film, the surface A method for forming a pattern structure for forming a self-assembled film, which includes a step of applying and baking the self-assembled film-forming composition on the lower layer film from which the layer has been removed, is also an object.
Here, as the solvent to be brought into contact with the lower layer film, the above solvent used for the lower layer film forming composition can be used. The surface layer of the lower layer film can be removed by contacting the solvent, and the removal of the surface layer can reduce the initial thickness of the lower layer film to 1/10 or less. By this step, the lower layer film can be made a thin film of 1 to 10 nm, for example.
2-ビニルナフタレン8.00g(ポリマー全体中に80モル%含有)、グリシジルメタクリレート1.05g(ポリマー全体中に10モル%含有)、ブトキシ(2-エチル)メタクリレート1.38g(ポリマー全体中に10モル%含有)、2,2’-アゾビスイソブチロニトリル0.6g、シクロヘキサノン38.03gを溶解させた後、この溶液を加熱し、85℃で約15時間撹拌した。得られたポリマーは下記式(1-1)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは、6,000であった。
8.00 g of 2-vinylnaphthalene (containing 80 mol% in the whole polymer), 1.05 g of glycidyl methacrylate (containing 10 mol% in the whole polymer), 1.38 g of butoxy (2-ethyl) methacrylate (10 in the whole polymer) (Mol% contained), 2,2′-azobisisobutyronitrile (0.6 g) and cyclohexanone (38.03 g) were dissolved, and the solution was heated and stirred at 85 ° C. for about 15 hours. The obtained polymer corresponded to the following formula (1-1). The weight average molecular weight Mw measured in terms of polystyrene by GPC was 6,000.
2-ビニルナフタレン12.0g(ポリマー全体中に70モル%含有)、グリシジルメタクリレート2.4g(ポリマー全体中に15モル%含有)、ブトキシ(2-エチル)メタクリレート3.2g(ポリマー全体中に15モル%含有)、2,2’-アゾビスイソブチロニトリル0.72g、プロピレングリコールモノメチルエーテルアセテート35.4gを溶解させた後、この溶液を加熱し、85℃で約19時間撹拌した。得られたポリマーは下記式(1-2)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは、8,380であった。
12.0 g of 2-vinylnaphthalene (containing 70 mol% in the whole polymer), 2.4 g of glycidyl methacrylate (containing 15 mol% in the whole polymer), 3.2 g of butoxy (2-ethyl) methacrylate (15 in the whole polymer) (2% mol), 2,2′-azobisisobutyronitrile (0.72 g) and propylene glycol monomethyl ether acetate (35.4 g) were dissolved, and the solution was heated and stirred at 85 ° C. for about 19 hours. The obtained polymer corresponded to the following formula (1-2). The weight average molecular weight Mw measured by GPC by polystyrene conversion was 8,380.
2-ビニルナフタレン20.0g(ポリマー全体中に80モル%含有)、ヒドロキシエチルメタクリレート4.2g(ポリマー全体中に20モル%含有)、2,2’-アゾビスイソブチロニトリル1.2g、プロピレングリコールモノメチルエーテルアセテート106.7gを溶解させた後、この溶液を加熱し、85℃で約15時間撹拌した。得られたポリマーは下記式(1-3)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは、4,150であった。
20.0 g of 2-vinylnaphthalene (containing 80 mol% in the whole polymer), 4.2 g of hydroxyethyl methacrylate (containing 20 mol% in the whole polymer), 1.2 g of 2,2′-azobisisobutyronitrile, After dissolving 106.7 g of propylene glycol monomethyl ether acetate, the solution was heated and stirred at 85 ° C. for about 15 hours. The obtained polymer corresponded to the following formula (1-3). The weight average molecular weight Mw measured in terms of polystyrene by GPC was 4,150.
2-ビニルナフタレン18.0g(ポリマー全体中に90モル%含有)、ヒドロキシエチルメタクリレート1.69g(ポリマー全体中に10モル%含有)、2,2’-アゾビスイソブチロニトリル0.98g、プロピレングリコールモノメチルエーテルアセテート48.4gを溶解させた後、この溶液を加熱し、85℃で約20時間撹拌した。得られたポリマーは下記式(1-4)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは、8,420であった。
18.0 g of 2-vinylnaphthalene (containing 90 mol% in the whole polymer), 1.69 g of hydroxyethyl methacrylate (containing 10 mol% in the whole polymer), 0.98 g of 2,2′-azobisisobutyronitrile, After 48.4 g of propylene glycol monomethyl ether acetate was dissolved, the solution was heated and stirred at 85 ° C. for about 20 hours. The obtained polymer corresponded to the following formula (1-4). The weight average molecular weight Mw measured by GPC by polystyrene conversion was 8,420.
2-ビニルナフタレン25.0g(ポリマー全体中に50モル%含有)、4-tert-ブトキシスチレン28.6g(ポリマー全体中に50モル%含有)、2,2’-アゾビスイソブチロニトリル2.69g、プロピレングリコールモノメチルエーテル131.3gを溶解させた後、この溶液を加熱し、85℃で約20時間撹拌した。得られたポリマーは下記式(1-5)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは、8,180であった。
2-vinylnaphthalene 25.0 g (containing 50 mol% in the whole polymer), 4-tert-butoxystyrene 28.6 g (containing 50 mol% in the whole polymer), 2,2′-azobisisobutyronitrile 2 .69 g and propylene glycol monomethyl ether (131.3 g) were dissolved, and the solution was heated and stirred at 85 ° C. for about 20 hours. The obtained polymer corresponded to the following formula (1-5). The weight average molecular weight Mw measured in terms of polystyrene by GPC was 8,180.
2-ビニルナフタレン18.0g(ポリマー全体中に60モル%含有)、メチルメタクリレート3.90g(ポリマー全体中に20モル%含有)、ヒドロキシエチルメタクリレート5.06g(ポリマー全体中に20モル%含有)、2,2’-アゾビスイソブチロニトリル1.35g、プロピレングリコールモノメチルエーテルアセテート66.0gを溶解させた後、この溶液を加熱し、85℃で約20時間撹拌した。得られたポリマーは下記式(1-6)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは、7,500であった。
2-vinylnaphthalene 18.0 g (containing 60 mol% in the whole polymer), methyl methacrylate 3.90 g (containing 20 mol% in the whole polymer), hydroxyethyl methacrylate 5.06 g (containing 20 mol% in the whole polymer) Then, 1.35 g of 2,2′-azobisisobutyronitrile and 66.0 g of propylene glycol monomethyl ether acetate were dissolved, and the solution was heated and stirred at 85 ° C. for about 20 hours. The obtained polymer corresponded to the following formula (1-6). The weight average molecular weight Mw measured in terms of polystyrene by GPC was 7,500.
2-ビニルナフタレン8.88g(ポリマー全体中に20モル%含有)、スチレン18.0g(ポリマー全体中に60モル%含有)、ヒドロキシエチルメタクリレート7.51g(ポリマー全体中に20モル%含有)、2,2’-アゾビスイソブチロニトリル1.72g、プロピレングリコールモノメチルエーテルアセテート84.4gを溶解させた後、この溶液を加熱し、85℃で約20時間撹拌した。得られたポリマーは下記式(1-7)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは、8,520であった。
8.88 g of 2-vinylnaphthalene (containing 20 mol% in the whole polymer), 18.0 g of styrene (containing 60 mol% in the whole polymer), 7.51 g of hydroxyethyl methacrylate (containing 20 mol% in the whole polymer), After dissolving 1.72 g of 2,2′-azobisisobutyronitrile and 84.4 g of propylene glycol monomethyl ether acetate, the solution was heated and stirred at 85 ° C. for about 20 hours. The obtained polymer corresponded to the following formula (1-7). The weight average molecular weight Mw measured in terms of polystyrene by GPC was 8,520.
アセナフチレン11.00g(ポリマー全体中に80モル%含有)、ヒドロキシエチルメタクリレート2.32g(ポリマー全体中に20モル%含有)、2,2’-アゾビスイソブチロニトリル0.40g、プロピレングリコールモノメチルエーテルアセテート32.01gを溶解させた後、この溶液を加熱し、85℃で約18時間撹拌した。得られたポリマーは下記式(1-8)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは、8,820であった。
11.00 g of acenaphthylene (containing 80 mol% in the whole polymer), 2.32 g of hydroxyethyl methacrylate (containing 20 mol% in the whole polymer), 0.40 g of 2,2′-azobisisobutyronitrile, propylene glycol monomethyl After dissolving 32.01 g of ether acetate, the solution was heated and stirred at 85 ° C. for about 18 hours. The obtained polymer corresponded to the following formula (1-8). The weight average molecular weight Mw measured in terms of polystyrene by GPC was 8,820.
ビニルカルバゾール11.00g(ポリマー全体中に80モル%含有)、ヒドロキシエチルメタクリレート1.85g(ポリマー全体中に20モル%含有)、2,2’-アゾビスイソブチロニトリル0.39g、シクロヘキサノン30.89gを溶解させた後、この溶液を加熱し、85℃で約19時間撹拌した。得られたポリマーは下記式(1-9)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは、6,950であった。
11.00 g of vinyl carbazole (containing 80 mol% in the whole polymer), 1.85 g of hydroxyethyl methacrylate (containing 20 mol% in the whole polymer), 0.39 g of 2,2′-azobisisobutyronitrile, 30 cyclohexanone After dissolving 89 g, the solution was heated and stirred at 85 ° C. for about 19 hours. The obtained polymer corresponded to the following formula (1-9). The weight average molecular weight Mw measured in terms of polystyrene by GPC was 6,950.
2-ビニルナフタレン5.23g(ポリマー全体中に60モル%含有)、メチルメタクリレート2.28g(ポリマー全体中に40モル%含有)、2,2’-アゾビス[2-メチル-N-(2-ヒドロキシエチル)プロピオンアミド(和光純薬 商品名VA-086)1.50gを、プロピレングリコールモノメチルエーテルアセテート54.60g、メタノール36.40gの混合溶媒に溶解させた。続いてこの溶液を加熱し、100℃で約12時間撹拌した。得られたポリマーは下記式(1-10)に相当した。そして、ポリマー末端には下記式(1-10-1)が結合していた。下記式(1-10-1)において、点線部分はポリマーとの結合を示す。GPCによりポリスチレン換算で測定される重量平均分子量Mwは、5,630であった。
2-vinylnaphthalene 5.23 g (containing 60 mol% in the whole polymer), methyl methacrylate 2.28 g (containing 40 mol% in the whole polymer), 2,2′-azobis [2-methyl-N- (2- 1.50 g of hydroxyethyl) propionamide (trade name VA-086, Wako Pure Chemical Industries, Ltd.) was dissolved in a mixed solvent of 54.60 g of propylene glycol monomethyl ether acetate and 36.40 g of methanol. The solution was subsequently heated and stirred at 100 ° C. for about 12 hours. The obtained polymer corresponded to the following formula (1-10). The following formula (1-10-1) was bonded to the polymer terminal. In the following formula (1-10-1), the dotted line portion indicates a bond with the polymer. The weight average molecular weight Mw measured in terms of polystyrene by GPC was 5,630.
2-ビニルナフタレン2.98g(ポリマー全体中に30モル%含有)、メチルメタクリレート4.52g(ポリマー全体中に70モル%含有)、2,2’-アゾビス[2-メチル-N-(2-ヒドロキシエチル)プロピオンアミド(和光純薬 商品名VA-086)1.50gを、プロピレングリコールモノメチルエーテルアセテート54.60g、メタノール36.40gの混合溶媒に溶解させた。続いてこの溶液を加熱し、100℃で約12時間撹拌した。得られたポリマーは下記式(1-11)に相当した。そして、ポリマー末端には下記式(1-11-1)が結合していた。下記式(1-11-1)において、点線部分はポリマーとの結合を示す。GPCによりポリスチレン換算で測定される重量平均分子量Mwは、5,850であった。
2.98 g of 2-vinylnaphthalene (containing 30 mol% in the whole polymer), 4.52 g of methyl methacrylate (containing 70 mol% in the whole polymer), 2,2′-azobis [2-methyl-N- (2- 1.50 g of hydroxyethyl) propionamide (trade name VA-086, Wako Pure Chemical Industries, Ltd.) was dissolved in a mixed solvent of 54.60 g of propylene glycol monomethyl ether acetate and 36.40 g of methanol. The solution was subsequently heated and stirred at 100 ° C. for about 12 hours. The obtained polymer corresponded to the following formula (1-11). The following formula (1-11-1) was bonded to the polymer terminal. In the following formula (1-11-1), the dotted line portion indicates a bond with the polymer. The weight average molecular weight Mw measured in terms of polystyrene by GPC was 5,850.
スチレン6.0g(ポリマー全体中に60モル%含有)、メチルメタクリレート2.0g(ポリマー全体中に20モル%含有)、ヒドロキシエチルメタクリレート2.0g(ポリマー全体中に20モル%含有)、2,2’-アゾビスイソブチロニトリル0.50g、プロピレングリコールモノメチルエーテル42.0gを溶解させた後、この溶液を加熱し、100℃で約16時間撹拌した。得られたポリマーは下上記式(1-12)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは、10,120であった。
6.0 g of styrene (containing 60 mol% in the whole polymer), 2.0 g of methyl methacrylate (containing 20 mol% in the whole polymer), 2.0 g of hydroxyethyl methacrylate (containing 20 mol% in the whole polymer), 2, After dissolving 0.50 g of 2′-azobisisobutyronitrile and 42.0 g of propylene glycol monomethyl ether, the solution was heated and stirred at 100 ° C. for about 16 hours. The obtained polymer corresponded to the above formula (1-12). The weight average molecular weight Mw measured by GPC in polystyrene conversion was 10,120.
合成例1で得た樹脂2gに、界面活性剤(DIC(株)製、品名:メガファック〔商品名〕R-30、成分はフッ素系界面活性剤)0.01g、プロピレングリコールモノメチルエーテルアセテート3.38g、シクロヘキサノン18.0g、γ-ブチロラクトン1.1gに溶解させ溶液とした。その後、孔径0.2μmのポリエチレン製ミクロフィルタを用いてろ過し、自己組織化膜の下層膜形成組成物の溶液を調製した。 Example 1
To 2 g of the resin obtained in Synthesis Example 1, 0.01 g of a surfactant (manufactured by DIC Corporation, product name: Megafac [trade name] R-30, component is a fluorosurfactant), propylene glycol monomethyl ether acetate 3 .38 g, cyclohexanone 18.0 g, and γ-butyrolactone 1.1 g were used as a solution. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film | membrane.
合成例2で得た樹脂2gに、界面活性剤(DIC(株)製、品名:メガファック〔商品名〕R-30、成分はフッ素系界面活性剤)0.01g、プロピレングリコールモノメチルエーテルアセテート15.8g、プロピレングリコールモノメチルエーテル6.8gに溶解させ溶液とした。その後、孔径0.2μmのポリエチレン製ミクロフィルタを用いてろ過し、自己組織化膜の下層膜形成組成物の溶液を調製した。 Example 2
To 2 g of the resin obtained in Synthesis Example 2, 0.01 g of a surfactant (manufactured by DIC Corporation, product name: Megafac [trade name] R-30, component is a fluorosurfactant), propylene glycol monomethyl ether acetate 15 0.8 g and dissolved in 6.8 g of propylene glycol monomethyl ether to prepare a solution. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film | membrane.
合成例3で得た樹脂2gに、テトラメトキシメチルグリコールウリル0.3g、ピリジニウム-p-トルエンスルホナート0.03g、界面活性剤(DIC(株)製、品名:メガファック〔商品名〕R-30、成分はフッ素系界面活性剤)0.002g、プロピレングリコールモノメチルエーテルアセテート6.8g、プロピレングリコールモノメチルエーテル15.8gに溶解させ溶液とした。その後、孔径0.2μmのポリエチレン製ミクロフィルタを用いてろ過し、自己組織化膜の下層膜形成組成物の溶液を調製した。 Example 3
To 2 g of the resin obtained in Synthesis Example 3, 0.3 g of tetramethoxymethylglycoluril, 0.03 g of pyridinium-p-toluenesulfonate, surfactant (manufactured by DIC Corporation, product name: Megafac [trade name] R- 30, component was fluorine surfactant (0.002 g), propylene glycol monomethyl ether acetate 6.8 g, propylene glycol monomethyl ether 15.8 g dissolved in solution. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film | membrane.
合成例4で得た樹脂2gに、テトラメトキシメチルグリコールウリル0.3g、ピリジニウム-p-トルエンスルホナート0.03g、界面活性剤(DIC(株)製、品名:メガファック〔商品名〕R-30、成分はフッ素系界面活性剤)0.002g、プロピレングリコールモノメチルエーテルアセテート13.5g、プロピレングリコールモノメチルエーテル9.0gに溶解させ溶液とした。その後、孔径0.2μmのポリエチレン製ミクロフィルタを用いてろ過し、自己組織化膜の下層膜形成組成物の溶液を調製した。 Example 4
To 2 g of the resin obtained in Synthesis Example 4, 0.3 g of tetramethoxymethylglycoluril, 0.03 g of pyridinium-p-toluenesulfonate, surfactant (manufactured by DIC Corporation, product name: Megafuck [trade name] R- 30, component was fluorine surfactant (0.002 g), propylene glycol monomethyl ether acetate 13.5 g, propylene glycol monomethyl ether 9.0 g was dissolved in solution. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film | membrane.
合成例5で得た樹脂2gに、テトラメトキシメチルグリコールウリル0.3g、ピリジニウム-p-トルエンスルホナート0.03g、界面活性剤(DIC(株)製、品名:メガファック〔商品名〕R-30、成分はフッ素系界面活性剤)0.002g、プロピレングリコールモノメチルエーテルアセテート13.5g、プロピレングリコールモノメチルエーテル9.0gに溶解させ溶液とした。その後、孔径0.2μmのポリエチレン製ミクロフィルタを用いてろ過し、自己組織化膜の下層膜形成組成物の溶液を調製した。 Example 5
To 2 g of the resin obtained in Synthesis Example 5, 0.3 g of tetramethoxymethylglycoluril, 0.03 g of pyridinium-p-toluenesulfonate, surfactant (manufactured by DIC Corporation, product name: Megafuck [trade name] R- 30, component was fluorine surfactant (0.002 g), propylene glycol monomethyl ether acetate 13.5 g, propylene glycol monomethyl ether 9.0 g was dissolved in solution. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film | membrane.
合成例6で得た樹脂2gに、テトラメトキシメチルグリコールウリル0.3g、ピリジニウム-p-トルエンスルホナート0.03g、界面活性剤(DIC(株)製、品名:メガファック〔商品名〕R-30、成分はフッ素系界面活性剤)0.002g、プロピレングリコールモノメチルエーテルアセテート13.5g、プロピレングリコールモノメチルエーテル9.0gに溶解させ溶液とした。その後、孔径0.2μmのポリエチレン製ミクロフィルタを用いてろ過し、自己組織化膜の下層膜形成組成物の溶液を調製した。 Example 6
To 2 g of the resin obtained in Synthesis Example 6, 0.3 g of tetramethoxymethylglycoluril, 0.03 g of pyridinium-p-toluenesulfonate, surfactant (manufactured by DIC Corporation, product name: Megafac [trade name] R- 30, component was fluorine surfactant (0.002 g), propylene glycol monomethyl ether acetate 13.5 g, propylene glycol monomethyl ether 9.0 g was dissolved in solution. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film | membrane.
合成例7で得た樹脂2gに、テトラメトキシメチルグリコールウリル0.3g、ピリジニウム-p-トルエンスルホナート0.03g、界面活性剤(DIC(株)製、品名:メガファック〔商品名〕R-30、成分はフッ素系界面活性剤)0.002g、プロピレングリコールモノメチルエーテルアセテート13.5g、プロピレングリコールモノメチルエーテル9.0gに溶解させ溶液とした。その後、孔径0.2μmのポリエチレン製ミクロフィルタを用いてろ過し、自己組織化膜の下層膜形成組成物の溶液を調製した。 Example 7
To 2 g of the resin obtained in Synthesis Example 7, 0.3 g of tetramethoxymethylglycoluril, 0.03 g of pyridinium-p-toluenesulfonate, surfactant (manufactured by DIC Corporation, product name: Megafuck [trade name] R- 30, component was fluorine surfactant (0.002 g), propylene glycol monomethyl ether acetate 13.5 g, propylene glycol monomethyl ether 9.0 g was dissolved in solution. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film | membrane.
合成例8で得た樹脂0.37gに、テトラメトキシメチルグリコールウリル0.07g、ピリジニウム-p-トルエンスルホナート0.01g、プロピレングリコールモノメチルエーテルアセテート26.6g、プロピレングリコールモノメチルエーテル3.0gに溶解させ溶液とした。その後、孔径0.2μmのポリエチレン製ミクロフィルタを用いてろ過し、自己組織化膜の下層膜形成組成物の溶液を調製した。 Example 8
Dissolved in 0.37 g of the resin obtained in Synthesis Example 8 in 0.07 g of tetramethoxymethyl glycoluril, 0.01 g of pyridinium-p-toluenesulfonate, 26.6 g of propylene glycol monomethyl ether acetate, and 3.0 g of propylene glycol monomethyl ether Solution. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film | membrane.
合成例9で得た樹脂0.37gに、テトラメトキシメチルグリコールウリル0.07g、ピリジニウム-p-トルエンスルホナート0.01g、シクロヘキサノン8.9g、プロピレングリコールモノメチルエーテルアセテート8.9g、プロピレングリコールモノメチルエーテル11.8gに溶解させ溶液とした。その後、孔径0.2μmのポリエチレン製ミクロフィルタを用いてろ過し、自己組織化膜の下層膜形成組成物の溶液を調製した。 Example 9
To 0.37 g of the resin obtained in Synthesis Example 9, 0.07 g of tetramethoxymethyl glycoluril, 0.01 g of pyridinium-p-toluenesulfonate, 8.9 g of cyclohexanone, 8.9 g of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether Dissolved in 11.8 g to prepare a solution. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film | membrane.
合成例4で得た樹脂0.2gに、プロピレングリコールモノメチルエーテルアセテート13.8g、プロピレングリコールモノメチルエーテル5.9gに溶解させ溶液とした。その後、孔径0.2μmのポリエチレン製ミクロフィルタを用いてろ過し、自己組織化膜の下層膜形成組成物の溶液を調製した。 Example 10
A solution was prepared by dissolving 10.2 g of propylene glycol monomethyl ether acetate and 5.9 g of propylene glycol monomethyl ether in 0.2 g of the resin obtained in Synthesis Example 4. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film | membrane.
合成例10で得た樹脂0.2gに、酢酸ブチル19.8gに溶解させ溶液とした。その後、孔径0.2μmのポリエチレン製ミクロフィルタを用いてろ過し、自己組織化膜の下層膜形成組成物の溶液を調製した。 Example 11
A solution was prepared by dissolving 10.2 g of butyl acetate in 0.2 g of the resin obtained in Synthesis Example 10. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film | membrane.
合成例11で得た樹脂0.2gに、酢酸ブチル19.8gに溶解させ溶液とした。その後、孔径0.2μmのポリエチレン製ミクロフィルタを用いてろ過し、自己組織化膜の下層膜形成組成物の溶液を調製した。 Example 12
A solution was prepared by dissolving 10.2 g of butyl acetate in 0.2 g of the resin obtained in Synthesis Example 11. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film | membrane.
比較合成例1で得た樹脂0.59gに、テトラメトキシメチルグリコールウリル0.15g、パラフェノールスルホン酸0.01g、プロピレングリコールモノメチルエーテルアセテート14.8g、プロピレングリコールモノメチルエーテル31.4gに溶解させ溶液とした。その後、孔径0.2μmのポリエチレン製ミクロフィルタを用いてろ過し、自己組織化膜の下層膜形成組成物の溶液を調製した。 Comparative Example 1
A solution prepared by dissolving 0.15 g of tetramethoxymethyl glycoluril, 0.01 g of paraphenolsulfonic acid, 14.8 g of propylene glycol monomethyl ether acetate, and 31.4 g of propylene glycol monomethyl ether in 0.59 g of the resin obtained in Comparative Synthesis Example 1. It was. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.2 micrometer, and prepared the solution of the lower layer film formation composition of a self-organization film | membrane.
実施例1~実施例9、比較例1で調製した自己組織化膜の下層膜形成組成物の溶液を、スピンコーターを用いてシリコンウェハ上に塗布した。ホットプレート上で240℃1分間焼成し、自己組織化膜の下層膜層(膜厚0.20μm)を形成した。これらの下層膜層をレジストに使用する溶剤であるプロピレングリコールモノメチルエーテル(PGME)及びプロピレングリコールモノメチルエーテルアセテート(PGMEA)に対する浸漬試験を行った。結果を表1に示した。残膜率はそれぞれの溶媒に60秒間浸漬し、浸漬前後の膜厚を測定し、(浸漬後の膜厚)/(浸漬前の膜厚)×100にて算出した結果である。 (Elution test for photoresist solvent)
The solutions of the self-assembled film underlayer film forming compositions prepared in Examples 1 to 9 and Comparative Example 1 were applied onto a silicon wafer using a spin coater. It baked on 240 degreeC on the hotplate for 1 minute, and formed the lower layer film layer (film thickness 0.20 micrometer) of a self-organization film | membrane. These lower layer layers were subjected to an immersion test in propylene glycol monomethyl ether (PGME) and propylene glycol monomethyl ether acetate (PGMEA), which are solvents used for resist. The results are shown in Table 1. The remaining film ratio is the result of immersing in each solvent for 60 seconds, measuring the film thickness before and after immersion, and calculating (film thickness after immersion) / (film thickness before immersion) × 100.
ドライエッチング速度の測定に用いたエッチャー及びエッチングガスは以下のものを用いた。
RIE-10NR(サムコ製):CF4
実施例1~実施例9、比較例1で調製した自己組織化膜の下層膜形成組成物の溶液を、スピンコーターを用いてシリコンウェハ上に塗布した。ホットプレート上で240℃1分間焼成し、自己組織化膜の下層膜形成組成物(膜厚0.20μm)を形成した。エッチングガスとしてCF4ガスを使用してドライエッチング速度を測定した。
また、クレゾールノボラック樹脂(市販品、重量平均分子量は4,000)の溶液を、スピンコーターを用いてシリコンウェハ上に205℃1分間焼成し、有機ハードマスク層(膜厚0.20μm)を形成した。エッチングガスとしてCF4ガスを使用して実施例1~実施例9、比較例1と同様にドライエッチング速度を測定し、実施例1~実施例9、比較例1と、有機ハードマスク層のドライエッチング速度との比較を行った。結果を表2に示した。速度比(1)は(実施例1~実施例9及び比較例1で用いた自己組織化膜の下層膜、240℃1分間焼成膜)/(クレゾールノボラック樹脂、205℃1分間焼成膜)のドライエッチング速度比である。 (Measurement of dry etching rate)
The following etchers and etching gases were used to measure the dry etching rate.
RIE-10NR (Samco): CF 4
The solutions of the self-assembled film underlayer film forming compositions prepared in Examples 1 to 9 and Comparative Example 1 were applied onto a silicon wafer using a spin coater. The composition was baked on a hot plate at 240 ° C. for 1 minute to form a lower film forming composition (film thickness 0.20 μm) of the self-assembled film. The dry etching rate was measured using CF 4 gas as the etching gas.
Also, a solution of cresol novolac resin (commercial product, weight average molecular weight is 4,000) was baked on a silicon wafer at 205 ° C. for 1 minute using a spin coater to form an organic hard mask layer (film thickness 0.20 μm). did. Using CF 4 gas as an etching gas, the dry etching rate was measured in the same manner as in Examples 1 to 9 and Comparative Example 1, and Examples 1 to 9 and Comparative Example 1 were used to dry the organic hard mask layer. Comparison was made with the etching rate. The results are shown in Table 2. The speed ratio (1) is (lower layer of self-assembled film used in Examples 1 to 9 and Comparative Example 1, fired film at 240 ° C. for 1 minute) / (cresol novolak resin, fired film at 205 ° C. for 1 minute) It is a dry etching rate ratio.
プロピレングリコールモノメチルエーテル32.33gにブロックポリマーであるポリスチレン/ポリ(メチルメタクリレート)コポリマー(POLYMER SOURCE INC.製、PS(18,000)-b-PMMA(18,000)、多分散度=1.07)1.0gを溶解させ、2質量%溶液とした後、孔径0.02μmのポリエチレン製ミクロフィルタを用いて濾過し、ブロックポリマーからなる自己組織化膜形成組成物の溶液を調製した。 (Preparation of block polymer)
Polypropylene glycol monomethyl ether (32.33 g), block polymer polystyrene / poly (methyl methacrylate) copolymer (manufactured by POLYMER SOURCE INC., PS (18,000) -b-PMMA (18,000), polydispersity = 1.07) ) After dissolving 1.0 g to obtain a 2% by mass solution, the solution was filtered using a polyethylene microfilter having a pore size of 0.02 μm to prepare a solution of a self-assembled film-forming composition comprising a block polymer.
実施例1~実施例7、比較例1で得られた自己組織化膜の下層膜形成組成物をそれぞれシリコンウェハ上に塗布し、ホットプレート上で240℃、1分間加熱し、自己組織化膜の下層に存在させる下層膜(A層)を得た。これらの下層膜の膜厚は200nmであった。
また、実施例8及び実施例9で得られた自己組織化膜の下層膜形成組成物をそれぞれシリコンウェハ上に塗布し、ホットプレート上で240℃、1分間加熱し、自己組織化膜の下層に存在させる下層膜(A層)を得た。これらの下層膜の膜厚は30nmであった。
さらに実施例10~実施例12で得られた自己組織化膜の下層膜形成組成物をそれぞれシリコンウェハ上に塗布し、ホットプレート上で240℃、1分間加熱した後、膜厚が30nmの下層膜を得た。その後、プロピレングリコールモノメチルエーテル/プロピレングリコールモノメチルエーテルアセテート=70/30の混合溶媒に60秒間浸漬し、自己組織化膜の下層に存在させる下層膜(A層)を得た。下層膜の膜厚はそれぞれ3nmであった。 (Evaluation of self-assembly of block polymer)
The underlayer film forming compositions of the self-assembled films obtained in Examples 1 to 7 and Comparative Example 1 were respectively applied on a silicon wafer and heated on a hot plate at 240 ° C. for 1 minute to form a self-assembled film. A lower layer film (A layer) to be present in the lower layer was obtained. The thickness of these lower layers was 200 nm.
In addition, the underlayer film forming composition of the self-assembled film obtained in Example 8 and Example 9 was applied onto a silicon wafer, and heated on a hot plate at 240 ° C. for 1 minute, to form a lower layer of the self-assembled film. The lower layer film (A layer) to be present in was obtained. The thickness of these lower layers was 30 nm.
Further, the underlayer film forming composition of the self-assembled film obtained in Examples 10 to 12 was applied on a silicon wafer, heated on a hot plate at 240 ° C. for 1 minute, and then a lower layer having a film thickness of 30 nm. A membrane was obtained. Then, it was immersed in a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate = 70/30 for 60 seconds to obtain a lower layer film (A layer) to be present under the self-assembled film. The thickness of each lower layer film was 3 nm.
ミクロ相分離構造を誘起させたシリコンウェハはLam製エッチャー(Lam 2300)を用い、エッチングガスとしてO2/N2ガスを使用して3秒間エッチングすることで、PMMA領域を優先的にエッチングし、続いて走査型電子顕微鏡(Hitachi S-9380)で形状を観察した。得られた結果を表3に示す。また、実施例1から得られた下層膜上に形成した自己組織化膜の走査型電子顕微鏡写真を図1に、比較例1から得られた下層膜上に形成した自己組織化膜の走査型電子顕微鏡写真を図2に、それぞれ示す。 (Observation of micro phase separation structure)
The silicon wafer in which the microphase separation structure is induced uses a Lam etcher (Lam 2300), and etches for 3 seconds using O 2 / N 2 gas as an etching gas, thereby preferentially etching the PMMA region, Subsequently, the shape was observed with a scanning electron microscope (Hitachi S-9380). The obtained results are shown in Table 3. A scanning electron micrograph of the self-assembled film formed on the underlayer film obtained from Example 1 is shown in FIG. 1, and the scanning type of the self-assembled film formed on the underlayer film obtained from Comparative Example 1 is shown in FIG. The electron micrographs are shown in FIG.
一方で比較例から得られた下層膜の結果に示されるように、多環ビニル構造であるビニルナフタレン等を含まない膜においては、上層の自己組織化膜におけるブロックポリマーを基板に対して垂直にミクロ相分離させることが出来ないとする結果となった。 As shown in Table 3, the lower layer films obtained from Example 1 to Example 12 are the upper layer self-assembled film, and the block polymer microphase separation structure composed of polystyrene and poly (methyl methacrylate) is formed on the substrate. It was possible to induce it vertically. In addition, the ability to induce perpendicularly to the substrate is not limited by components other than the polycyclic vinyl structure, as shown in the components contained in the lower layer films obtained from Examples 1 to 12. It was.
On the other hand, as shown in the result of the lower layer film obtained from the comparative example, in the film not containing vinyl naphthalene having a polycyclic vinyl structure, the block polymer in the upper self-assembled film is perpendicular to the substrate. The result was that microphase separation could not be performed.
Claims (18)
- ポリマーの全単位構造あたり多環芳香族ビニル化合物の単位構造を0.2モル%以上有するポリマーを含むことを特徴とする、自己組織化膜の下層膜形成組成物。 A composition for forming a lower film of a self-assembled film, comprising a polymer having a unit structure of a polycyclic aromatic vinyl compound of 0.2 mol% or more per total unit structure of the polymer.
- 前記ポリマーが、ポリマーの全単位構造あたり芳香族ビニル化合物の単位構造を20モル%以上有し、且つ該芳香族ビニル化合物の全単位構造あたり多環芳香族ビニル化合物の単位構造を1モル%以上有するポリマーであることを特徴とする、請求項1に記載の自己組織化膜の下層膜形成組成物。 The polymer has a unit structure of aromatic vinyl compound of 20 mol% or more per total unit structure of the polymer, and 1 mol% or more of unit structure of polycyclic aromatic vinyl compound per total unit structure of the aromatic vinyl compound The composition for forming a lower layer film of a self-assembled film according to claim 1, wherein the composition is a polymer having.
- 前記芳香族ビニル化合物が、各々置換されていてもよいビニルナフタレン、アセナフチレン又はビニルカルバゾールを含み、且つ、前記多環芳香族ビニル化合物がビニルナフタレン、アセナフチレン又はビニルカルバゾールである、請求項2に記載の自己組織化膜の下層膜形成組成物。 The said aromatic vinyl compound contains each vinyl naphthalene, acenaphthylene, or vinyl carbazole which may be substituted, and the said polycyclic aromatic vinyl compound is vinyl naphthalene, acenaphthylene, or vinyl carbazole. A composition for forming a lower layer film of a self-assembled film.
- 前記芳香族ビニル化合物が、置換されていてもよいスチレンと、各々置換されていてもよいビニルナフタレン、アセナフチレン又はビニルカルバゾールとを含み、前記多環芳香族ビニル化合物がビニルナフタレン、アセナフチレン又はビニルカルバゾールである、請求項2又は請求項3に記載の自己組織化膜の下層膜形成組成物。 The aromatic vinyl compound contains optionally substituted styrene and each optionally substituted vinyl naphthalene, acenaphthylene, or vinyl carbazole, and the polycyclic aromatic vinyl compound is vinyl naphthalene, acenaphthylene, or vinyl carbazole. A composition for forming a lower layer film of a self-assembled film according to claim 2 or claim 3.
- 前記芳香族ビニル化合物が、置換されていてもよいスチレンと、各々置換されていてもよいビニルナフタレン、アセナフチレン又はビニルカルバゾールであり、前記多環芳香族ビニル化合物が、各々置換されていてもよいビニルナフタレン、アセナフチレン又はビニルカルバゾールである、請求項2乃至請求項4のうちいずれか1項に記載の自己組織化膜の下層膜形成組成物。 The aromatic vinyl compound is styrene that may be substituted, vinyl naphthalene, acenaphthylene, or vinyl carbazole, each of which may be substituted, and vinyl that each of the polycyclic aromatic vinyl compounds may be substituted. The underlayer film-forming composition for a self-assembled film according to any one of claims 2 to 4, which is naphthalene, acenaphthylene, or vinylcarbazole.
- 前記芳香族ビニル化合物が、多環芳香族ビニル化合物のみからなり、前記芳香族ビニル化合物が、各々置換されていてもよいビニルナフタレン、アセナフチレン又はビニルカルバゾールである、請求項2乃至請求項5のうちいずれか1項に記載の自己組織化膜の下層膜形成組成物。 The said aromatic vinyl compound consists only of a polycyclic aromatic vinyl compound, and the said aromatic vinyl compound is the vinyl naphthalene, acenaphthylene, or vinyl carbazole which may each be substituted among Claim 2 thru | or 5 The underlayer film forming composition of the self-assembled film according to any one of the above items.
- 前記ポリマーが、ポリマーの全単位構造あたり芳香族ビニル化合物の単位構造を60~95モル%有する、請求項2乃至請求項6のうちいずれか1項に記載の自己組織化膜の下層膜形成組成物。 The composition for forming a lower layer film of a self-assembled film according to any one of claims 2 to 6, wherein the polymer has 60 to 95 mol% of an aromatic vinyl compound unit structure per total unit structure of the polymer. object.
- 前記ポリマーが、更に架橋形成基を有する単位構造を有する、請求項1乃至請求項7のうちいずれか1項に記載の自己組織化膜の下層膜形成組成物。 The underlayer film-forming composition for a self-assembled film according to any one of claims 1 to 7, wherein the polymer further has a unit structure having a crosslinking group.
- 前記架橋形成基がヒドロキシ基、エポキシ基、保護されたヒドロキシ基又は保護されたカルボキシル基である、請求項8に記載の自己組織化膜の下層膜形成組成物。 The composition for forming a lower layer film of a self-assembled film according to claim 8, wherein the cross-linking group is a hydroxy group, an epoxy group, a protected hydroxy group or a protected carboxyl group.
- 更に架橋剤を含む、請求項1乃至請求項9のうちいずれか1項に記載の自己組織化膜の下層膜形成組成物。 The composition for forming a lower layer film of a self-assembled film according to any one of claims 1 to 9, further comprising a crosslinking agent.
- 更に酸又は酸発生剤を含む、請求項1乃至請求項10のいずれか1項に記載の自己組織化膜の下層膜形成組成物。 The underlayer film forming composition for a self-assembled film according to any one of claims 1 to 10, further comprising an acid or an acid generator.
- 前記自己組織化膜が、有機モノマー(a)を単位構造として含む有機ポリマー鎖(A)と、有機モノマー(a)とは異なるモノマー(b)を単位構造として含み且つ該有機ポリマー鎖(A)に結合してなるポリマー鎖(B)とを含むブロックポリマーより成る膜である、請求項1乃至請求項11のうちいずれか1項に記載の自己組織化膜の下層膜形成組成物。 The self-assembled film includes an organic polymer chain (A) containing an organic monomer (a) as a unit structure, a monomer (b) different from the organic monomer (a) as a unit structure, and the organic polymer chain (A). The underlayer film-forming composition for a self-assembled film according to any one of claims 1 to 11, wherein the composition is a film made of a block polymer containing a polymer chain (B) bonded to.
- 前記ブロックポリマーが、ポリスチレン(A)とポリメチルメタクリレート(B)、ポリスチレン(A)とポリイソプレン(B)、ポリスチレン(A)とポリブタジエン(B)、ポリスチレン(A)とポリジメチルシロキサン(B)、ポリスチレン(A)とポリエチレンオキシド(B)、又はポリスチレン(A)とポリビニルピリジン(B)の各組み合わせからなるブロックポリマーである、請求項12に記載の自己組織化膜の下層膜形成組成物。 The block polymer is polystyrene (A) and polymethyl methacrylate (B), polystyrene (A) and polyisoprene (B), polystyrene (A) and polybutadiene (B), polystyrene (A) and polydimethylsiloxane (B), The underlayer film-forming composition for a self-assembled film according to claim 12, which is a block polymer comprising each combination of polystyrene (A) and polyethylene oxide (B), or polystyrene (A) and polyvinylpyridine (B).
- 基板上に請求項1乃至請求項13のうちいずれか1項に記載の自己組織化膜の下層膜形成組成物を塗布し焼成し下層膜を形成する工程、該下層膜上に自己組織化膜形成組成物を塗布し焼成する工程を含む、自己組織化膜を形成するパターン構造の形成方法。 A process for forming a lower layer film by applying and baking a lower layer film-forming composition of a self-assembled film according to any one of claims 1 to 13 on a substrate, a self-assembled film on the lower layer film A method for forming a pattern structure for forming a self-assembled film, comprising a step of applying and baking a forming composition.
- 基板上に請求項8又は請求項9に記載の自己組織化膜の下層膜形成組成物を塗布し焼成し下層膜を形成する工程、該下層膜に溶剤を接触させて該下層膜の表面層を除去する工程、該表面層を除去した下層膜上に自己組織化膜形成組成物を塗布し焼成する工程を含む、自己組織化膜を形成するパターン構造の形成方法。 A step of applying and baking the underlayer film forming composition of the self-assembled film according to claim 8 or 9 on a substrate to form an underlayer film, and contacting the solvent with the underlayer film to form a surface layer of the underlayer film A method for forming a pattern structure for forming a self-assembled film, comprising: a step of removing the surface layer; and a step of applying and baking a self-assembled film-forming composition on the lower layer film from which the surface layer has been removed.
- 自己組織化膜の下層膜形成組成物を塗布し焼成し下層膜を形成する工程の前に、基材上に下地膜を形成する工程を含む、請求項14又は請求項15に記載のパターン構造の形成方法。 The pattern structure according to claim 14 or 15, comprising a step of forming a base film on a substrate before the step of applying and baking the underlayer film forming composition of the self-assembled film to form the lower layer film. Forming method.
- 前記下地膜が反射防止膜又はハードマスクである、請求項16に記載のパターン構造の形成方法。 The pattern structure forming method according to claim 16, wherein the base film is an antireflection film or a hard mask.
- 請求項14乃至請求項17のうちいずれか1項に記載のパターン構造の形成方法により得られたデバイス。 A device obtained by the pattern structure forming method according to any one of claims 14 to 17.
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US14/651,998 US10508181B2 (en) | 2012-12-18 | 2013-12-13 | Bottom layer film-formation composition of self-organizing film containing polycyclic organic vinyl compound |
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JP2014553113A JPWO2014097993A1 (en) | 2012-12-18 | 2013-12-13 | Composition for forming underlayer of self-assembled film containing polycyclic aromatic vinyl compound |
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PCT/JP2013/083492 WO2014097993A1 (en) | 2012-12-18 | 2013-12-13 | Bottom layer film-formation composition of self-organizing film containing polycyclic organic vinyl compound |
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US (1) | US10508181B2 (en) |
EP (1) | EP2937391A4 (en) |
JP (1) | JPWO2014097993A1 (en) |
KR (2) | KR102357731B1 (en) |
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Also Published As
Publication number | Publication date |
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CN104854205B (en) | 2018-12-28 |
KR20150097516A (en) | 2015-08-26 |
CN104854205A (en) | 2015-08-19 |
JPWO2014097993A1 (en) | 2017-01-12 |
EP2937391A4 (en) | 2016-08-31 |
US10508181B2 (en) | 2019-12-17 |
KR102357731B1 (en) | 2022-02-08 |
KR20200106560A (en) | 2020-09-14 |
EP2937391A1 (en) | 2015-10-28 |
TWI638235B (en) | 2018-10-11 |
TW201430501A (en) | 2014-08-01 |
US20150322219A1 (en) | 2015-11-12 |
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